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By W. Joseph Schlitt

The characteristics of successful heap and dump leach operations are first reviewed in a general sense. Then attention is focussed on solution management as the key operating parameter in leaching. The first part of this study includes a detailed conceptual analysis of fluid flow. This identifies the relationships between the flow parameters and the chemical and physical properties of the rock. Then these relationships are extended to practical systems in order to establish optimum application rates and solution distribution methods for heaps and dumps. The study shows that there is a maximum effective application rate, qmax, that can be used without causing solution short circuiting. This rate is a function of the minimum permeability in the heap or dump. The expression for qmax is qmax (gal/ft2/hr)[~]0.9 k (darcies). Here k is the appropriate permeability coefficient. Using this equation, qmax is found to be on the order of 1 gal/ft2/hr (4 cm/hr) for a typical heap or dump leach operation.

Jan 1, 1984

By Gilbert Soler

Page Introduction. By Gilbert Soler.........................657 Deoxidation of Basic Open-hearth Steel. By T. S. Washburn.............658 Slag-metal-oxygen Relationships in the Basic Open-hearth and Electric Processes. By J. S. Marsh. (With discussion)...........................672 The Total Oxygen Content of Plain Carbon Open-hearth Steel during Deoxidation and Teeming. By Michael Tenenbaum and C. C. Brown. (With discussion)......685 The Occurrence of Oxygen in Liquid Open-hearth Steel—Sampling Methods. By T. E. Brower and B. b. Larsen..........................712 Effect of Deoxidation on the Strain-sensitivity of Low-carbon Steels. By H. K. Work and G. H. Enzian. (With discussion)........................723 The Relation among Aluminum, Sulphur, and Grain Size. By C. E. Sims.......734 Some of the papers and discussions that appear on the following pages were presented at the meeting of the Iron and Steel Division in Cleveland, Ohio, on Wednesday, October 18, 1944. with L. F. Reinartz and H. K. Work as Chairmen; the remainder were scheduled for the New York Meeting of the Institute in February 1945, which was canceled.

Jan 1, 1945

By R. M. Treco

The effect of small additions of oxygen on the hardness, density, and lattice parameters of high purity zirconium has been investigated. Precision parameter values and density of oxygen-free zirconium are given as: a,, - 3.2258 kX units, C = 5.1373 kX units, O23 = 6.507 g per cc. THE effect of oxygen on the hexagonal-phase lattice constants of pure zirconium is of interest for several reasons. The extensive hardening effect of oxygen noted by previous investigators' must be due in part to the lattice distortion accompanying its introduction and possibly to the preferred position of the oxygen atoms. De Boer and Fast' have shown that oxygen is taken into solid solution in large amounts, appearing to occupy an interstitial position. These authors also found that expansion of the lattice was not uniform since the a axis attained a constant value after the addition of 10 atomic pct while the c axis continued to expand. It was thought in the present work that this expansion of the zirconium lattice with increasing amounts of oxygen

Jan 1, 1954

By B. C. Craft

The outstanding event of the year 1932 in this area was the intensive drilling activity in the Zwolle field of Sabine Parish, Louisiana. More new development work was undertaken and completed than during the previous year. This was due in part to the increased price of oil and in a Includes 19 parishes: Beauregard, Bienville, Bossier, Caddo, Caldwell, Catn-houla, Claiborne, Concordia, DeSoto, Grant, Lincoln, Morehouse, Natchitoches, Ouachita, Red River, Richland, Sabine, Union, Webster. B H. K. Shearer: Oil and Gas Development in South Arkansas, North Louisiana and Mississippi in 1931. Trans. A. I. M. E. (1932) 98, 159. a Includes 14 counties: Ashley, Columbia, Dallas, Drew, Hot Springs, Lincoln, LnFayette, Little River, Miller, Ouachita, Pike, Sevier, Scott and Union. * H. K. Shearer: Oil and Gas Development in South Arkansas, North Louisiana and Mississippi in 1931. Trans. A. I. M. E. (1932) 98, 159. part to the fact that production is below local market demands. Exploration during 1932 resulted in the discovery of a new oil field and a new gas

Jan 1, 1933

By W. L. Freyberger

In a study of the kinetics of flotation of coal, employing a single-cell continuous flotation system, Jowett and Safvi1 pointed out that it was experimentally impossible to float all of the coal which could be floated in a batch tests. On the other hand, deBruyn and Modi, in a discussion of their paper, suggested that under certain conditions the recovery of floatable material from a similar one-cell continuous system would have been 100%.2 Both of these pairs of authors make the assumption that a state of perfect mixing exist in the flotation cell. This assumption, usually made by investigators studying flotation kinetics in a continuous system, has been confirmed experimentally on several occasions. The work is summarized by Arbiter and Harris.3 It is the purpose of this note to demonstrate that, for conditions of perfect mixing, one of two conditions exist: 1) the recovery of floatable material is 100%, and the flotation is infinitely fast, or 2) the recovery of floatable material must be less than 100%. This theorem can be proved simply in the following manner: 1) If recovery, R, of the floatable material is 100%, the concentration in the tailing must be zero. This follows from the definition of recovery as

Jan 1, 1964

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By J. D. Verhoeven

The effectiue distriblltion coefficient has been Measured in a series of vertical, normal freezing experirtzents with large current densities passing through the solid-liquid interface. The results indicate that the effect of the current on solute redistribution is due to electvotransport in the liquid. The high currents produced extensive mixing in the liquid which was considerably reduced by solidifying in small lubing. Analysis of the convection indicates that it probably vesulls from a horizontal temperature gradient produced by the Joule heating- of the electvic crirver~t. Due to the strong dependence of this convection upon the specimen radius, it is conclnded that only for specit~ens with radii of less than somewhere between 1 and 2 mm wilt electric field freezing be getlerally effec-tire at enhancing the purification of zone-melting experittierats in loe-melting alloys. Experiments on 0.8-mm lubes illustrate some interesting potential applications of this techniqne as a means of solute control on smcrll specimens. In a number of papers published within the last few years'-4 it has been found that passage of large dc currents through the solid-liquid interface of a freezing alloy produces a change in the solute redistribution accompanying the solidification. It had been predicted theoretically by Hucke et al.s and by Pfann and Wagner that such an effect would occur as the result of electrotransport within the liquid boundary layer at the solid-liquid interface. These authors independently derived the following relation between the effective distribution coefficient and the variables of the process: Where k0 is the equilibrium distribution coefficient, V is the mobility of the solute relative to the solvent, E is the electric field intensity, D is the solute diffusion coefficient, R is the rate of interface motion, and 6 is the boundary layer thickness. Both groups of authors show that this equation predicts the possibility of extending the purification ability of zone-melting experiments by the addition of an electric current. However, there are other effects in addition to electro-transport which could be produced by the high dc current and might, perhaps, invalidate the applicability of Eq. [I]. For example, high electric current might affect the interface reaction or perhaps the equilibrium distribution which was assumed to exist at the interface. It was the purpose of this work to determine the applicability of Eq. [I] by systematically investigating a simple system for which all of the necessary parameters were known. It was of particular interest for speculating on the potential usefulness of this technique to determine the maximum practical field intensities obtainable, and the effect of these high fields upon convective mixing in the liquid. The initial work in this study was published in a previous paper3 which will be referred to as I. In that work, a current density of 2000 amps per sq cm was used with specimen diameters of 5 mm. The results gave a qualitative confirmation of Eq. [I.], and also showed that a large amount of convective mixing was produced in the liquid by the current. The present study is an extension of that work to smaller specimen diameters and higher current densities. Two points were overlooked in I and will be emphasized here: a) the value of ko has not been well-established in the Sn-Bi system and b) the observed convection could be due to thermal convection produced from the Joule heating. EVALUATION OF k0 To evaluate Eq. [ I.] it is necessary to know the value of the equilibrium distribution coefficient, k,. Tn I the value of k, was taken as 0.3 from a published phase diagram.7 According to ansen' the best data on the phase boundaries of the Sn-Bi system are those of Davidson.5 The data of Davidson give a k, value ranging from 0.21 to 0.25 for the compositions studied in this work, or an average value of around 0.23. In a recent publication, Rigaud and Tougas'10 determined ko by means of a solidification technique. For an alloy of approximately the same composition as that used in this work they obtained a ko value of 0.39. Hence, there is considerable uncertainty in the value of ko and, consequently, a series of experiments were made to determine k, more accurately.

Jan 1, 1968

By Morris E. Fine, Richard A. Kloske

The stress-strain beha1,ior in tension of Au-Ag alloy single crystals containing nominally 1,3, 5, 95, 97, and 9.9 at. pct Ag was studied uS strain role and lektlperalure down lo 4.2K. A slrain aging yield hob lc,rrs observed on aging under stress in the temperature range 30° lo 75°C. The species diffusing to the dislocation is thought to be a divacancy-solute complex wilh /he. solute then pinning the dislocation by short-Range ovdering and possibly Suzuki locking. At room tempevullcve the critical reso1ved shear stress .follo~c.s an empirical equation of the form tc = A +Bc' where A and B are 90 and 420 ,g per sy mm tor gold base alloys and 60 and 510 g p~r sq )11ttz .tor si1ver base alloys. This strengthening was attributed to a long-range size ejtect. The alloy slrenglliening at i.2'K is greafer than at room temperature. The additional atrloutzf was altribuled lo a uwak skovl-range i?~levacIion between the solute and dislocallon cove. The activation energy .tor deformation a/ 4.Z0h7 decreases on alloying. 11 increases irr other fee systetns. hi the 5 at. pcl Air-Ag- alloy in pmvlicular there is very extensive easy glide and lavge overshooting- of the synmetry line at 4.Z°K. There is also u sharp decrease in the vale of. strain hardenitlg near the widdle of stage II with the new rate bezng abold the sarne as tlzal In easy glide. This uws attributed to a sudden reduction of activity on the pvitrrarg sgstertr. In Au-Ag alloys the critical resolved shear stress Tc. at room temperature is essentially a parabolic function of atomic concentration:' the 50 at. pct Ag-50 at. pct Au alloy is about 10 times stronger than the pure metals. This strengthening occurs in spite of the similarity in valence and atomic size. Solid-solution strengthening in fcc metals is characteristically greater at low temperatures than at room temperature. In Ag-10 at. pct Au and Au-10 at. pet Ag; r, (20.4K)/Tc (300°K) is 2.3 and 2.5. respectively.- compared to 1.2 in pure silver.3 Suzuki' and Flinn5 explained the alloy strengthening at room temperature as a combination of Suzuki locking and short-range order hardening. The agreement between the computed and measured strengthening was very good: however, in Ag base-A1 alloys Hendrickson and Fine6 concluded that Suzuki locking resulted mainly in a yield drop effect. Recent reviews of the solid-solution strengthening in fcc metals by Fleischer2 and Haasen8, 9attributed the strengthening at room tenl-perature to the combined effect of atom nlisfit and change in shear modulus 011 the long-range stress field surrounding a dislocation. The parameter used by Fleischer was The shear tnoduli of Ag-0 to 6 at. pct Au alloys were measured by Pur-wins. Labusch. and Haasen.In While addition of 4 at. pct Au caused an appreciable increase in the C,, elastic constant. there was a decrease on increasing the solute to 6 at. pct Au: C,, and C :: were not measured in the 6 at. pct alloy. The greater solution hardening at low temperatures implies the presence of short-range interactions between the solute atoms and dislocations These include size and electronegativity effects. Whether the extra alloy strengthening at low temperatures is due to locking or friction hardening is still a controversy."".' In the present research the stress-strain behavior of Au-Ag single crystals containing 1 to 5 at. pct Ag and 1 to 5 at. pct Au was measured vs strain rate and temperature down to 4.2' K. Particular attention was paid to yield drop effects. These have not been previously reported. PROCEDURES The alloys were supplied by the Engelhard Industries. Inc.. as strips 0.050 by 0.250 by 12 in. The compositions are given in Table I. Single crystals were grown under static vacuum using a traveling molten zone technique. Crucibles shaped to the size of the strips were made of high-purity graphite prebaked for 24 hr at 1100°C in vacuum. The crucible and its charge were placed in

Jan 1, 1970

[I-Institute of Metals Division PAUL D. MERICA, Chairman ZAY JEFFRIES, Vice-chairman W. M. CORSE, Secretary General Committee ROBERT J. ANDERSON H. C. JENNISON L. W. SPRING WILLIAN K. FRANK DAVID LEVINGER R. L. SUHL J. R. FREEMAN, JR. PAUL McKINNEY R. F. WOOD]

Jan 1, 1928

By N. W. Lord

The process of molten-zone refining is analyzed for long ingots and many zone passages. Formulas are derived which give the resultant impurity distribution in terms of finite series. A comparison with the approximate procedure of Hamming is given. HE physical principles and applications of an extremely physicalprinciple efficient form of metallurgical refinement has been described by Pfann. The purpose of the present paper is to describe a method of analyzing exactly the particular program used which enables the segregation effect to be predicted for any number of molten-zone passages in a long ingot. The method is applied to the particular case of refinement of an ingot whose impurity initially is uniformly distributed throughout its length. A number of molten zones of equal length are passed through the ingot effecting a radical redistribution of impurity. Pfann has indicated an approximate method, due to R. W. Hamming, of calculating the resultant concentration after each successive zone pass for a particular value of the segregation constant defined in his paper. Here a solution will be presented in terms of the number of zone passes and the segregation constant. The expression, though cumbersome, is exact and susceptible to ordinary numerical computation procedures. The results of a similar computation using the procedure of Hamming are presented in a table together with the exact results of the present method. The discrepancy in terms of absolute concentrations is tabulated for the first eight zone-lengths. To establish the notation (which follows that of Pfann1 as closely as possible) and physical basis of the analytical equations, the physical model and principal assumptions may be reviewed. An alloy of two elements, where there is formed a continuous range of solid solutions, usually does not melt as a simple compound. Rather, a temperature is reached where the solid solution is in heterogeneous phase equilibrium with a liquid solution of different composition. The temperature dependence of these equilibrium compositions forms part of the phase diagram. For very small concentrations of a solute B in a solvent A, this usually takes the form of Fig. 1. Sometimes the solidus and liquidus slope upward. This corresponds to a segregation constant (defined below) which is greater than unity. The segregation constant is now defined as k = Cn(x)/CnI(x) [1] where C,,(x) is the impurity concentration in the solid ingot at distance x during the nth passing of a molten zone and Cnl (x) is the impurity concentration of the liquid zone from which the solid at dis- tance x is formed (see Fig. 4 of ref. 1.) C (x) remains the same after passage of the zone. The constant k may be either greater or less than unity in general. Purification in the former case is effected only in a finite ingot and in the portion that is melted last. For k less than unity purification is effected even in an infinite ingot. The method which follows gives, in the former case, the successive increases in impurity concentration and, in the latter case, the successive decreases in concentration. The general case of impurity redistribution will be considered first, and purification will be discussed later on. The analysis rests on the following assumption: The movement of the zone is too rapid to allow appreciable atomic rearrangement in the solid sections and too slow to disturb the uniform impurity distribution in the liquid zone characteristic of equilibrium. Hence, the composition in the solid at the left solidifying interface will be determined by Eq. 1 while the impurity concentration of the liquid zone will be uniform throughout its length. The reasoning which follows closely parallels that of Appendix 11 in Pfann&apos;s paper. It is reviewed here for the case of the nth zone pass in order to make clear the meaning of an operator essential to the present method. Fig. 4 of ref. 1 shows the movement of a molten zone of length 1 in an ingot of total length d. Each Cn(x) can be determined from the condition that the amount of solute added to the zone during an incremental advance, dx, is due to the melting in of a solid portion C(x)dx and the freezing out of kCnl(x), that is d I —r- CnL (x) dx = Cn-1 (x+l)- kCnL (x) dx or, in terms of Cn(x) d k k —— C,(x) +—c.(x) =— Cn-1 (x + l). [2] dx l l This, of course, is derived from the main assumption, the fact that 1 is constant, and that the total impurity content previously present up to x + 1 is constant . A correction has to be made for the region (d — nl) < x < d. This is due to the zone length changing during the passage of the solidifying interface beyond x = d — 1. Since the general solution would be too complicated otherwise, only the region 0 < x < d — nl is considered. The general solution of Eq. 2 is

Jan 1, 1954

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10&apos; dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900&apos; to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.&apos; Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,&apos; the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-&apos;9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.&apos; In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970

By C. N. Reid

Slip-line studies on deformed chromium single cvystals showed the usual bcc behavior. At room temperatuve, cross slip was prevalent—slip was not confined to a given plane, but the slip direction was (111). At -10O0K, slip occuvred on (110) planes, twins on(112) planes, and cleavage on (1001 planes. A single-crystal tensile specimen with an axis close to [011] showed a pronounced yield drop and high strain rate sensitivity which zclere used to derive relevant parame tevs in a dislocation dynamics treatment. Transmission electron microscope studies confirmed the existence of (110) slip planes and showed ecidence of loops punched out by precipitates and of grown-in dislocations promoting tangling. OF recent years experimental studies have been made of the deformation characteristics of single-crystal molybdenum and tungsten, but very little has been published on the behavior of single-crystal chromium. During a study of the mechanical properties of chromium, single-crystal studies were made which have already been partially described.&apos; However, additional information was generated which was not directly relevant to the main theme of Ref. 1, and, therefore, was not reported. In view of the need for complete documentation of deformation modes, the experimental observations made on the deformation of single-crystal chromium are summarized here, together with an electron-microscope study of the associated dislocation structures. It was found that, in terms of the deformation modes, chromium is a conventional bcc metal, showing a very pronounced yield-point phenomenon. Further, it was found that the flow strength of these crystals is very sensitive to the strain rate. Finally, the crystals were observed to contain many unidentified precipitates, which often were associated with prismatic dislocation loops. EXPERIMENTAL METHODS Single crystals were grown from rods of wrought chromium by the method of zone annealing. Rods of "1/4in.-diam were supported vertically in an argon atmosphere while an induction coil was moved up the rod at 1 in. per hr. The power was adjusted to just below that required for melting, and the process produced single crystals in about 30 pct of the rods used. The orientations of the crystals, in general, lay near [011] and are summarized in Fig. 1. Before this treatment, the wrought material contained 35 pprn C, 68 ppm O, and 12 ppm N.* An analyzed single crystal *Usual metallic impurities found in iodide chromium are: Al, 5 ppm; Ca, A ppm; Cu, 2 ppm; Fe, 75 ppm; Yg, 0.5 ppm; Yn, < 3 ppm; Mo, < 3 ppm; Ni, 4 ppm; Si, < 20 ppm; Ti, < 1 ppm; V, 4 ppm; Zr, < 3 ppm. contained 10 pprn C, 79 ppm O, and 50 pprn N. Tension and compression specimens were shaped from the crystals by mechanical grinding, followed by the electrolytic removal of about 0.010 in. from the surface in a perchloric/acetic acid bath. All specimens had a gage length of 0.75 in., and tension specimens had a diameter of 0.100 in., while that of the compression samples was 0.200 in. Mechanical tests were carried out at a rate of 1.3 pct per min, and temperatures below 0°C were attained by means of a nitrogen cryostat similar to that of Wessel.2 EXPERIMENTAL RESULTS Modes of Deformation. In addition to the tensile properties of these crystals, which are described in Ref. 1, deformation markings on the surface were studied. Crystals A and F, Fig. 1, were deformed in tension at 300°K to 10 and 16 pct strain, respectively. The surfaces contained visible slip lines, about 1 C( apart, composed of both straight and wavy segments. They did not define a single plane, and so determination of the slip plane was not possible. However, the slip direction was deduced by comparing the axial orientations of the crystals before and after deformation. Fig. 2 is representative, and shows that the axis ro-

Jan 1, 1968

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,&apos; however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.&apos; Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation&apos; in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.&apos; For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

Institute of Metals Division PAUL D MERICA, Chairman ZAY JEFFRIES, Vice-chairman W M CORSE. Secretary General Committee ROBERT J ANDERSON H C JENNISON L W SPRING WILLIAM K FRANK DAVID LEVINGER R L SUHL J R FREEMAN, JR. PAUL McKINNEY R F WOOD STANISLAUS SKOWRONSKI

Jan 1, 1923

Coal Transport Via Pipe Line Claimed Feasible Moving coal via pipe line is a project proposed by the U. S. Bureau of Mines. A pipe line 100 miles long capable of transporting 5000 tons of coal a day with water could be built for about $10 million. The cost of moving the coal 100 miles would be between $1.28 and $2.01 a ton.

Jan 9, 1951

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors&apos; conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors&apos; article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.&apos;); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors&apos; reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

Established as a Division December 15, 1948 Evan Just, Chairman Richard J Lund, Past Chairman Granville S. Borden, Vice-Chairman J K Richardson, Vice-Chairman S H Williston, Vice-Chairman Allan Matthews, Secretary-Treasurer National Security Resources Board 17th and Pennsylvania Ave, N W Washington 25, D C

Jan 1, 1952