Search Documents

By Edward Keller

Someone some time ago remarked that some chemists still insist on telling us how to determine copper by the electrolytic method. The writer must confess that he believes that everything is not known definitely as yet as to how the exact amount of copper is determined in such material as purest commercial electrolytic copper. Some of us are not yet convinced that the pure copper atom is at all times deposited from an acid solution and that no oxygen or hydrogen will, under certain conditions, accompany it. Difficulties with impurer material are frequent, but erroneous results are not always apparent, since these do not speak so readily for themselves as those in the first case. By this is meant that if a chemist finds 100 per cent. of copper in electrolytic copper it is pretty certain that he perceives the result to be wrong, while if he finds 0.1 per cent. of copper too much in a very impure material he is far more likely to be unconscious of his error. These, in a wide experience, are frequent happenings and the writer has always looked with interest to publications on this subject. In turn, he feels justified in giving to others a few of his own observations. Up to a few years ago there were two methods of electrolytic copper assay in technical use, which had in common, that the amount of copper deposited on the cathode did not exceed 2 g., and they differed in that, for the one a large sample1 (20 to 80 g.) was taken from the general sample by a splitting device, dissolved, and from the solution a small portion (to contain 1 or 2 g. of copper) measured out for the electrolytic deposition; in the other method the copper was determined, generally in 1-g. portions of the separated coarse and fine portions of the sample, all of which passed a 16 or 20-mesh screen, being accomplished by a 40-mesh screen,

Jan 1, 1914

By D. N. Witman

ONE of the special uses to which the electric furnace has been put recently is the melting of an alloy of nickel and cast iron for the production of electrical-resistance grids. The metal sections of these grids, Fig. 1, are quite uniform for each pattern, but there is, among the various patterns, a variety of thicknesses. The cross sections vary from 1/2 by 3/16 in. to as small as 1/8 by 1/8 in. The electrical resistance f a perfect casting lies within 10 per cent. above or below the fixed listed resistance for each pattern. Good molding is essential to success in the making of these grids, for with absolutely correct metal, a variation of 0.01 in. in width and thickness of section on some of the patterns may mean as much as 12 or 14 per cent. variation in resistance. The service for which these castings are intended demands that the metal, even in the smallest castings, be very soft, showing an open, gray, highly graphitic structure in order that they may be resistant to shock, and stand up well under rough usage. The metal used for this purpose is a gray iron alloyed with 4 to 5 per cent. of nickel, which element, when the composition of the alloy is correct, imparts toughness and pliability to the metal and helps to overcome the tendency of metal to run white and become brittle because of the rapid cooling action of the sand mold. When cold, these castings can be twisted into various shapes, taking a permanent set without breaking. The alloy has approximately double the electrical resistance of ordinary cast iron. The metal specification is as follows: PER CENT. Silicon 2.40 to 2.60 Sulfur Under 0.05 Phosphorus Under 0.08 Manganese Under 0.40 Total carbon 3.60 to 4.00 Nickel 4.00 to 5.00 Copper 0.50 to 0.70

Jan 8, 1921

By Alexander L. Field

In the light of the experimental data on equilibrium for the reaction C + FeO = Fe + CO in molten steel recently obtained by Kinzel and Egan,l it is necessary to revise current theories regarding the nature of equilibrium between carbon and FeO in the basic open-hearth furnace. According to the measurements of these investigators the equilibrium constant m for the above reaction for a pressure of dissolved CO equal to 1 atm. is equal to 0.0005 at 1550" C., when concentrations of carbon and FeO are expressed in percentages by weight. Their work also shows that, with the pressure of CO fixed at 1 atm., not only is the product of carbon and FeO constant, but carbon and FeO are each independently constant—a circumstance which might have been predicted from theoretical considerations. At 1550" C., carbon is constant at about 0.025 per cent. and FeO at about 0.020 per cent., with the pressure of dissolved CO equal to 1 atm., the product of these two constants being equal to the originally mentioned constant of 0.0005. Available data on the dissolved FeO content of samples taken from the metal bath at practical slag-metal equilibrium prove that this FeO content is determined solely by temperature and the effective FeO content of the slag. The distribution constant r at 1550" C., as determined by Herty, Gaines, Larsen, Simkins, Geruso and Watkins2 is equal to 0.0086. A slag would have to contain 0.020 = 2.3 per cent. effective 0.0086 FeO or less in order to prevent the metal from containing more dissolved FeO than that required for equilibrium with CO at 1 atm. pressure. Such low percentages of FeO are never found in basic open-hearth slags at the completion of a heat when rate of carbon drop has become practi-

Jan 1, 1930

By James Douglas

In discussing the waste upon which hinges, or is supposed to hinge, so largely the preservation of our national resources, the conclusions reached would be more reliable if actual experience were consulted, and fewer deductions were drawn from general statements, which are often the product of the imagination. It cannot be questioned that the value of by-products has .not been sufficiently appreciated by us, and that our tardiness in recovering the useful ingredients of the escaping gas of our coke-ovens is one of the most glaring instances of shortcoming in that direction. And yet even for that sin there is some palliation in the immature condition of affiliated industries. I presume that it is admitted, without argument, that, except under very exceptional conditions, all the elements cannot be recovered from most of the ores or natural products which we treat. While it is a shame that the by-products from our coke-ovens should be dissipated, Edward W. Parker's report to the U. S. Geological Survey for 19061 supplies a fairly good excuse in justification of this appalling waste. He says (pp. 773 to 774.): " What has been already commented on in previous reports about the slowness of manufacturers to change from the better known but wasteful beehive practice to the by-product recovery method of coke manufacture is particularly emphasized in the statistics presented in this chapter. For it would appear from the table following that the construction of by-product ovens had about come to a standstill, especially when the records for the preceding five years are taken into consideration. At the close of 1901, when there were only 1,165 by-product ovens completed in the United States, there were 1,533 in course of construction, 498 of which were completed during the following year. At the close of 1902, 1,346 retort ovens were building, 293 of which were added to the completed plants in 1903. At the close of 1903, 1,335 new ovens were building and 954 of these

Jan 1, 1910

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication' an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,' only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement' was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By J. Kostuik, M. J. de Bastiani

The method of mining the uranium orebody at Denison mine in the Elliot Lake district of Ontario is discussed. Details of the development of haulage-ways and rooms are giuen, as well as methods of ore haulage. The milling and beneficiation stages are noted briefly. Located in the Elliot Lake mining district of Canada, the Denison mine lies between Sudbury to the east and Sault Ste. Marie to the west, Fig. 1. This area is overlain by Huronian sediments filling a basin in the Keewatin basement complex. Subsequent folding of these sediments developed a synclinal structure, known locally as the Quirke Lake Trough, which forms the northern portion of the now famous big Z structure, the geological trademark of this region. Plunging to the west and extending nine miles from the granite outcropping in the north to the Keewatin lava contact to the south, the syncline has dips of 10" to 45" on the north limb and 10" to 20" on the south limb, Fig. 2. The Denison orebody, located on the north limb of the syncline, lies between 800 and 3000 ft below the surface. The main ore zone is within 50 ft of the Missisagi-Keewatin contact (see Fig. 3), and it varies in thickness from 6 to 32 ft. This ore zone has a composite dip of 19" to the south and is composed primarily of two pyritized conglomerate beds separated by a band of pebbly quartzite stratum. The upper conglomerate bed of the main zone varies from 2 to 15 ft in thickness, while the lower conglomerate varies from 2 to 12 ft. Over extended areas, mining is carried out over the entire section comprising the two conglomerate layers and intercalated quartzite; in other areas, the conglomerates are selectively mined, depending on the thickness of the quartz-ite. The ore zone contains approximately 6 pct sulfides and 80 pct silica. The predominant uranium-bear ing minerals are brannerite, uraninite, and an unidentified mineral (probably thucolite). Some of the uneconomic metallic minerals identified to date are pyrite, pyrrhotite, and chalcopyrite. MINE LAYOUT Shafts: Underground exploration and development (Fig. 4) were performed through two shafts 1/2 mile apart. The No. 1 shaft, sunk to a depth of 1856 ft with the main station established at the 1600-ft ore level, is a 250-sq ft, 5-compartment shaft capable of handling 4500 tpd. Two 5x5-1/2-ft compartments serviced by a 12-ft diam double-drum hoist, are used for hoisting 190-cu-ft bottom-dump skips in balance. A 30-man cage, offset by a counterbalance, operates within a 5-1/2x11-1/2-ft compartment. The fifth compartment is used as a manway, pipe, and cable-way. This shaft is also provided with an intermediate pumping station used during the initial mining phase as well as loading-pocket and spill-pocket installations and pumping facilities. The 480-sq ft No. 2 shaft, located down-dip from No. 1 shaft, has a 2776-ft depth. Serving as the main hoisting shaft with a maximum capacity of 9000 tpd, it has eight compartments, four of which are used for hoisting ore in 10-ton capacity bottom-dump skips. These four compartments, measuring 5x6-ft in section, are serviced by two 12-ft diam double-drum semi-automatic hoists. A 50-man cage is operated in a 15x8-ft compartment, and it is counterbalanced by a 12-ton weight. Two compartments are used for ventilation, manway, electric cables, and pipes. A station was constructed at the 1325-ft horizon of the No. 2 shaft for relay pumping. The main sta-

Jan 1, 1961

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By W. R. Hibbard

It has been proposed1 on the basis of slip and flow that the ideal deformation texture of drawn wire for face-centered cubic metals is a (111) direction parallel to the wire axis. Under these considerations, an intermediate [loo] texture is permissible but should eventually change to the stable [Ill] orientation. This theory does not explain why copper and its alloys containing up to about 30 pct nickel, 5 pct zinc and 1 pct aluminum were found to have a double [Ill], [100] texture, while alloys with at least 8 pct zinc and 2 pct aluminum developed essentially a single [Ill] texture.1,2 It does suggest, however, that the [loo] component of the former alloys should disappear with additional deformation.3 Some evidence exists to support this suggestion. Howald4 reported that annealed copper wire previously drawn 93.8 pct and 98.5 pct developed a single [Ill] texture. Since, in wire, the drawn and annealed textures are similar, these wires probably had a single [Ill] deformation texture before annealing. In addition, although cold rolled polycrystalline copper and 80-20 brass were found to form different types of pole figures,5,6 single crystals of these metals when rolled from the stable (110) [112] orientation were found to produce essentially the same polo figure.7.8 It may be, therefore, that while the addition of solute elements changes the path by which the final texture is obtained, the final texture is not changed. Experimental Results The wires remaining from the previous investigation1 already drawn about 50 pct reduction in diameter were further drawn to 86 pct and then to 96.4 pct total reduction in diameter. The textures were determined after these stages by transmission X ray photograms taken with a copper K-alpha beam rotated 0 degrees toward the wire axis. It was found that the ratio of the [111].] and [100] intensities of the double texture in copper and its alloys containing 0.94 pct aluminum, 30.70 pct nickel, 2.61 pct zinc and 4.99 pct zinc increased from about 3:l for the 50 pct reduction to about 9:l for the 86 pct reduction. After 96.4 pct reduction, these wires exhibited essentially a single [lll] texture. Summary Thus, the drawn wire deformation texture of copper and its alpha solid solution alloys containing aluminum, nickel or zinc is essentially a single [Ill] texture as predicted by theoretical considerations of slip and flow.' For copper and its alloys containing up to about 1 pct aluminum, 5 pct zinc and at least 30 pct nickel, an intermediate [loo] component is found after about 50 pct reduction in diameter, but disappears after about 95 pct reduction in diameter. For alpha solid solution alloys containing at least about 2 pct aluminum and 8 pct zinc the single [Ill] texture is developed considerably more easily and is found after about 50 pct reduction in diameter. No explanation of this compositional effect is apparent. Similar work is contemplated for cold rolled and cold compressed alloys. References 1. w. R. Hibbard, Jr. and M. K. Yen: Trans. AIME 175, 126. Metals Tech., Feb. 1948, TP 2334. 2. W. R. Hibbard, Jr. and D. E. Trout, 11: Trans. AIME 185, 620. Jnl. of Melals, Sept. 1949, TN 18. 3. W. R. Hibbard. Jr.: Disc. of R. M. Brick's paper on Deformation Textures, ASM Symp. on Cold Working of Metals, Oct. 1948. 4. T. S. Howald: Disc. of Ref. 1. Trans. AIME, 175, 126. Melals Tech. Aug. 1948, TP 2449. 5. R. M. Brick, D. L. Martin and R. P. Angier: Trans. ASM (1943) 31, 675. 6. 0. Dahl and F. Pawlek: Zlsch. Melall. (1936) 28, 266. 7. C. S. Barrett and F. W. Steadman: Trans. AIME (1942) 147, 57. 8. J. E. Burke and C. S. Barrett: Trans. AIME 175, 106. Melals Tech., Feb. 1948. TP 2327.

Jan 1, 1950

By Jim D. Mote, Eugenia M. Howard, Willis L. Barmore, John E. Dorn

The effect of stress and temperature on the creep rate of Ag-33 at. pct A1 and Ag-33 at. pct Al-1 at. pct Zn for prismatic slip was determined over a range of temperatures from 440º to 700°K. The alloys exhibited a brief initial inverted transient creep over which the creep rate increased slightly to a steady-state value which depended only on the stress and temperature, regardless of the previous strain history. The steady-state creep rates were found to be given by: where the activation energy is independent of the stress and strain and agrees fairly well with that estimated for diffusion. The observed creep behavior was shown to be in qualitative agreement with a model based on the stress-induced local disordering in the vicinity of a dislocation. OVER the past fifteen years, considerable progress has been made in correlating the experimen-entally observed plastic behavior of pure metals over each temperature range with one or more of a series of theoretical strain-rate controlling dislocation mechanisms. Despite the current interest in the plastic behavior of intermediate phases and inter metallic compounds, however, very little has been done in identifying the operative dislocation mechanisms in these materials. It is anticipated that the plastic behavior of intermediate phases can be rationalized in terms of the same dislocation mechanisms that are appropriate to pure metals and a solid solutions, provided the additional complexities arising from crystal structure, bonding, long-range order, short-range order, and defect lattices are taken into account. As part of a more extensive investigation on the plastic behavior of intermediate phases, Mote, Tanaka, and Dorn1 recently reported on the effect of temperature on the yield strength for prismatic slip in the hexagonal Ag-33 at. pct A1 intermediate phase as recorded in Fig. 1: Over Region I the deformation was observed to take place as a result of the thermally-activated Peierls mechanism, and over Region II the athermal disordering mechanism applied. The experimental data at that time, however, were not sufficiently extensive to identify the thermally activated mechanisms operative over Region III. It is the purpose of this investigation to attempt to identify the mechanisms that are operative over this high-temperature region. It will be shown that the same mechanism operates all over Region Ill, although the activation energy for this mechanism is in good agreement with that for diffusion, the process cannot be attributed either to the motion of jogged screw dislocations or the climb of edge dislocations. The results, however, are in good qualitative agreement with stress-induced disordering localized at dislocations. EXPERIMENTAL PROCEDURE The alloys studied in this investigation were prepared from silver, aluminum, and zinc (each of purity greater than 99.995 pet) by induction melting under an argon atmosphere and chill casting in a copper mold. Rectangular bar single crystal specimens (1/4 by 1/8 in. in cross-sect ion) of Ag-33 at. pct Al were grown in vacuum by a modified Bridgman technique. Similar Ag-33 at. pct Zn specimens were produced by an identical technique employing an argon atmosphere. The specimens were so oriented that the angle 90-Xo between the tensile axis and the normal to the prismatic plane and the angle A, between the tensile axis and the slip direction were 45 ± 1 deg. The effect of a change in temperature on the creep rate and a change in stress on the creep rate were determined over the temperature range

Jan 1, 1963

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5'9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1' at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.' It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By J. W. Downey, M. V. Nevitt

MUELLER and Knott' have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962

By M. B. Bever, A. K. Jena

Equations for the heat effects of additions of mixtures of multicomponent phases to a solution have been derived in terms of the enthalpy interaction coefficients. By these equations and the measured composition dependence of the heat effects on addition of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions, values of the enthalpy in-teraction coefficients in tin-rich solutions at 541°K have been obtained. Analysis of these results in terms of the regular solution theory and the quasichemical theory suggests that near the melting point of the solvent association in the solution becomes important. SEVERAL recent papers have discussed the nature of dilute solutions on the basis of measured enthalpy interaction coefficients. l-3 These coefficients contribute to the understanding of the constitution of solutions and can be used for the evaluation of thermo-dynamic data of multicomponent systems. Their experimental determination, however, is laborious. This communication reports values of the enthalpy interaction coefficients of silver, cadmium, and gold in liquid tin-rich solutions obtained from the measured heat effects of additions of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions. These measurements were made in the course of the determination of the heats of formation of Ag-Cd solid solutions reported in a concurrent publication.4 THE HEAT EFFECT OF AN ADDITION TO A SOLVENT This analysis is concerned with the addition of a mixture of multicomponent phases from the temperature To to a solvent of known composition at temperature T. If Nmixture << Nsolvent, where N designates the gram-atoms involved, the heat effect per g-atom of mixture added can be expressed as (HT - HT )i = difference in heat contents of component element i in the mixture at T and To Q = heat effect on solution of the mixture at temperature T Also1 Q = S Xi [2] where ?Hi ,T,x = relative partial enthalpy per g-atom of i in solution at temperature T and composition of the solution x x = average of the atom fractions of the added material in solution before and after the addition The relative partial enthalpy ?Hi per g-atom of an element i in a dilute solution composed of a solvent 1 and the solutes j = 2, ... m is related to the interaction coefficients by the following equation5 ?Hi - ?Hi-?Hi,x1-1 + S n1ixj+ . . . +S...S...S nrixn2... Xnji...Xnmm+... [3] vhere Xj = atom fraction of solute j in the solution nri = the rth order enthalpy interaction coefficients, which can also be represented by the more general designation5 L(i)n2,n3...nm and nj may have any positive integral value or zero. For identification of various rth order interaction coefficients, nri is written as nn2i2,...nij,...nmm. Eqs. [1], [2], and [3] combine to give the following general equation for the heat effect on addition of a small quantity of a mixture to a large quantity of a dilute solution n = _?ga ?Ha,To + ? Xi(HT - HT o)i a. i + ?xi?Hi,X,i?1 + ??xnjixj + . . . + ???. . .?. . .?xinrix2n2. . . xnji. . . xnmm+ . . . [4] The first term on the right-hand side of this equation is the heat of decomposition at the addition temperature of the phases present in the mixture, the second term is the heat required to raise the temperature of

Jan 1, 1970

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet&apos; 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References &apos; E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. &apos;D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, &apos; E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800&apos;C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By Garth M. Crosby

Seven mines with important production records in the Coeur d&apos;Alene lie adjacent to the Gem stocks -the Frisco (Gem), Hercules, Interstate, Rex (Sixteen to One), Success (Granite), Sunset, and Tamarack. Old records are incomplete, but avail- able data given in Table I show these mines have produced 10,550,721 tons of ore containing more than 50 million oz of silver, more than 1.5 billion lb of lead, and about 1 billion lb of zinc (approximately 1.25 million tons of lead and zinc combined). Average ore grade is 4.8 oz of silver per ton, 7.2 pct Pb, and 4.6 pct Zn. This impressive production represents about 12 pct of the District&apos;s yield. At present metal prices, with modern beneficiation, the gross value would be more than $400 million.

Jan 7, 1959

South Dakota State School of Mines, Rapid City, S. D. C C O&apos;Harris,-President. A number of technical bulletins have been issued at the South Dakota State School of Mines but, unfortunately, most of them are out of print and as this directory is concerned only with available publications, the following are all that are now to be had Bulletin 11, A bibliography of the geology and mining interests of the Black Hills region (1917), no charge; 14, The geology, mineralogy, and scenic features of Custer State Park (1926), 40 cents plus postage on 1 lb ; 15, The Tertiary mineralization of the northern Black Hills (1927), charge, postage on 1 1b.; 16, The mineral wealth of the Black Hills t418 pages) (1929), 80 cents plus postage on 3 lb

Jan 1, 1933

By Rodney P. Smith

The diffusivity of carbon (0.1 wt pct C) in Fe-Nz alloys (0 to 100 pct Ni) has been determined for the temperature range 860° to 1100°C. As a function of nickel content, the diffusivity has a maximum near 60 pct Ni (the maximum diffusivity being about 1.3 times that in the absence of nickel); the activation energy has a maximum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The difference between the minimum activation energy and that in iron is about 3000 cal pev g-atom; Do has a minimum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The results cannot be rationalized by an approximate thermodynamic treatment. THE diffusivity of carbon has been determined in a number of iron alloys over a limited concentration range. It seemed desirable to investigate a system which allows an extended range of alloy composition within a single-phase region. The Fe-Ni system is ideal in this respect, in that all alloys from 100 pct Fe to 100 pct Ni are fee in a convenient temperature range.&apos; The carbon diffusivity was determined by a decar-burization method. The experimental procedure was identical with that used to determine the diffusivity of carbon in y Fe-Co alloys.2 The experimental data are given in Table I. A small correction (order of a few percent) has been made to the measured carbon loss to correct for the carbon lost from the ends of the cylinders.&apos; Since the diffusivity of carbon varies with carbon content the measured diffusivity is an average value for a carbon content between zero (surface) and that at the center of the sample at the end of the decarburization periods. In making the correction in D to 0.1 wt pct C it is assumed that the measured D corresponds to the arithmetical mean of the carbon content at the surface and at the center of the sample at the end of the decarburization period.3 Since this correction is small (<4 pct in D) and since for our decarburization times the changes in carbon content at the center of the sample was small the mean carbon content could have been taken as half the initial value. It is further assumed that the change in D with carbon content for the alloys is the same as that for the diffusion of carbon in iron. From the data of Wells, Batz, and Mehl4 and of smith5 the correction of D from the mean carbon content to 0.1 wt pct C is 0.3 (0.1 - mean wt pct C). The results for iron are given in Ref. 2. Within the experimental error log Do.l%C for each alloy is a linear function of 1/T; the constants for the equation determined by the method of least squares are given in Table I. The deviations of the experimental points from the least-squares line are of the order of 2 pct in D. A comparison of our results for the diffusivity of carbon in nickel with those of other investigations is shown in Fig. 1. The lower curve in Fig. 1 is a linear extrapolation of values calculated* from the equation of Diamond6 for the relaxation time (temperature range 100° to 500°C). The results indicate a small increase in the activation energy over the temperature range 100° to 1400°C; however, it is difficult to say whether the change in Q is real or experimental error. Certainly the change in Q is less than the variation of 5 kcal per g-atom in the diffusivity of carbon in a iron.6 The experimental data for all the alloys are plotted in Fig. 2. As a function of nickel content the diffusivity has a maximum near 60 wt pct Ni at all temperatures investigated and possibly a minimum between 80 and 90 wt pct Ni for temperatures below 1000°C. The activation energy, Q, and log Do are plotted as a function of the nickel content in Fig. 3. Due to the limited temperature range of our experiments neither Q nor Do can be determined precisely; the activation energies appear to be consistent to ±0.3 kcal per g-atom; however the deviation from the absolute values may be considerably larger, see Table II. The Do values probably have little significance. The solid line for Do in Fig. 3 represents the values required to reproduce the experimental values for D when Q has values represented by the upper solid line The diffusivity of carbon may be expressed in terms of the mobility B22, the activity coefficient r2,

Jan 1, 1967

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

A. L. BLOMFIELD, ? Colorado Springs, Colo. (written discussion?).¬I congratulate the author on bringing out a paper of real service to the profession. His contention of uniform size in balls is borne out by my own experience; in coarse crushing at the Golden Cycle in 6 by 6-ft. (1.8 by 1.8-m.) ball-mills we unquestionably gain by screening out the small balls once or twice a month. The point of gaging the ball size to be used by the uniformity of screen sizing is of particular interest. The necessity of sufficient return feed from classifier to the ball-mill is sound and clearly shown. In connection with this, I wish two further points had been gone into as thoroughly: (1) The effect of the quality of classification. In general, it is true that the smaller the per cent. of undersize in the feed the more effective is the mill&apos;s work. This is true on a bucking board, in tube-mills, ball-mills, and grinding pans. Given the possibility of returning. a full-feed load to any mill, it has been my experience that the effective work in the grinder is almost proportional to the quality of the return feed. (2) Again speaking generally, the shorter the tube-mill the greater is the quantity of return feed necessary to keep it loaded. The classification thus keeps the oversize in the mill more free from finished product and thus the crushing more efficient. It is very easy to overload any long mill with too much return

Jan 4, 1919