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By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By C. H. Schack

Extractive metallurgy techniques currently employed to recover silver from primary ores and secondary scrap were reviewed and evaluated to identify and delineate metallurgical problems whose resolution would increase the supply of silver from domestic materials. The survey revealed that practically all primary silver is recovered by froth flotation concentration of various types of ores, followed by smelting and refining of the separate lead, copper, and zinc concentrates. Silver losses during the complex processing are, with rare exception, inconsequential. Furthermore, any silver production gain from base metal ores, which contribute about two-thirds of the total primary silver, is directly dependent in improvement in the market for the base metals. Statistical data on new and old silver scrap are wholly inadequate to make reliable conclusions about scrap processing problems and the possibility of increasing the recovery of silver from the many forms of secondary silver- bearing materials. The available information indicates (1) that efficient silver reclamation practices are employed by the larger users of silver, and (2) that recovery of additional secondary silver involves solution of problems of collection rather than of processing. Several possibilities exist for limited increases in silver production from primary ores by improvement in metallurgical practices. Specifically, research is needed to (1) solve the problem of recovering silver from the copper ores of the Copper Range district, Michigan; and (2) devise economically feasible methods for recovery of silver from presently marginal or submarginal ores that because of grade, location, and frequently complex nature cannot presently be exploited by conventional techniques.

Jan 1, 1965

By L H. Warren

The types of equipment available for generating a plasma have been reviewed. The efficiency and potential of the plasma generating equipment used in performing extractive metallurgical reactions have been determined. A general classification of the reactions that might be per-formed in a plasma has been proposed. Experimental work done on extractive metallurgical plasma reactions, heat transfer between the plasma and solids, and the quench of the products of plasma reaction has been summarized. From the preliminary results it appears that the high-intensity are or the transpiration-cooled anode plasma torch offer the most promising areas for further research. C ONSIDERABLE world-wide research effort is currently being devoted to the development of processing technologies which employ the new high-temperature generating devices that have appeared over the past few years. The plasma flames produced by these devices offer the potential for subjecting materials to any single gas or mixture of gases at temperatures up to 20,000°K. With these conditions available, many reactions in extractive metallurgy,

Jan 1, 1965

By T. C. Davis

Nine organic derivatives of fluorine, silicon, boron, and aluminum were purified for thermodynamic studies using distillation, zone melting, and gas liquid chromatography, The unusual properties of these compounds required the development of special techniques for handling and purification. To determine purities of purified samples, new techniques for analyzing spectral data were developed.

Jan 1, 1965

By J A. Gilliand

Mineralogical cross sections of orebodies on the 300-,600- and 900-foot levels of the Coronation mine have been interpreted in terms of centers of mineralization. The maximum concentration of chalcopyrite occurs closest to these centers, with pyrite and pyrrhotite concentrated some distance away. The magnetite concentrations are farthest removed from the centers. A hydrous halide fluid model is established. Attempts to explain the observed mineralogy by the action of temperature gradients on the fluid model were unsuccessful. Likewise, the action of diffusion alone on the fluid model cannot explain the observed mineral distribution. The concept of attenuation is introduced-i.e., the rate of diffusion of a particle species is related to the product r2 I/ M, the attenuation coefficient, where r is the particle radius and M its molecular weight. Attenuation, acting on the fluid model alone, will not produce the observed mineral distribution, but, when considered together with the action of temperature gradients, the observed mineralogy can be well explained by the combined effects of these two processes on the assumed fluid model.

Jan 1, 1965

By H. A. Schrecengost

Information presented herein was gathered by examination of 29 fluidized-bed thermal coal dryers and by conferences with manufacturers and users of such equipment to determine what safety features could b incorporated in design, installation, and op ration to minimize fire and explosion hazards. Fire and explosion hazards are inherent in certain types of coal dryers in that high temperatures are employed; the sizes and volatility of material handled are capable of propagating explosions; and drying gases are seldom, if ever, low enough in oxygen content to prevent ignitions of dust clouds, distilled gases, or their combinations. This is especially true for fluidized-bed dryers in which the coal is dried in air suspension and in which atmospheric air is constantly introduced to temper the heated furnace gases. Occurrence of fires on hated bedplates, in dust collectors, and in hot gas inlets was common in nearly all the dryers examined. Forceful explosions which produced external effects had occurred in 11 (39 percent), and internal "puffs" or ?bumps? had occurred in at least 24 (79 percent) of the plants examined in the study.

Jan 1, 1965

By Clark F. Grain

The monoclinic to tetragonal inversion of zirconium dioxide was studied by single-crystal X-ray methods, high-temperature X-ray diffractometry, and differential thermal analysis. The unusual features of the inversion, such as no definite transition Lperature, hysteresis, and athermal kinetics, were confirmed for powders who mean crystallite size was greater than 1,000 A. Samples of mean crystallite size below 1,000 A displayed classical kinetics, obeying a logarithmic rate law. A detailed mechanism based on Ubbelohde&apos;s theory of continuous phase transformations was proposed which is consistent with all the experimental facts.

Jan 1, 1965

By James S. Browning

The Bureau of Mines conducted laboratory batch and pilot plant flotation tests to determine the technical feasibility of recovering commercial-grade mica from a California micaceous schist. Best results in the laboratory batch tests were obtained using sodium carbonate and sodium silicate for pH control and quartz depression, and a combination of fatty acid and cationic reagents as the mica collector. In continuous pilot plant flotation tests, an alkaline fatty acid-cationic method recovered about 70 percent of the mica in a concentrate analyzing 95.6 percent mica.

Jan 1, 1965

By F J. Kelly

A chemical process, based on laboratory investigations, is proposed for the production of high-purity niobium oxide from a pyrochlore-perovsk1te flotation concentrate produced from ore obtained at the Oka, Quebec property of Columbium Mining Products Limited. The method developed included the decomposition and dissolution of the flotation concentrate with hot, concentrated sulphuric acid. The dissolved niobium was purified and concentrated by a solvent extraction step, using methyl isobutyl ketone as the extractant. The niobium was recovered from the extractant with ammonium fluoride solution from which niobium oxide was precipitated with ammonia. Finally, the filtered and washed precipitate was calcined. Ninety-six per cent of the niobium was recovered in a product analysing 99.9 per cent Nzo.. The reagent cost was in the range of $1.00 to $1.25 per pound of niobium recovered. Introduction OVER the past few years, Columbium Mining Products Limited has been engaged in the development of a niobium-bearing mineral deposit in the vicinity of Oka, Quebec. One phase of this program resulted in a flotation process capable of producing concentrates containing up to 50 per cent Nb205? Flotation pilot-plant

Jan 1, 1965

By John Nagy

Results of initial research by the Bureau of Mines are given on the dust explosion hazard of float coal and on the related factors of occurrence, rate of production, sampling techniques, transport, and deposition of float coal. Tentatively, it is suggested that where float coal deposits prevail, a mini-mum of 80 percent incombustible be maintained in the top 1/8-inch layer to neutralize the explosion hazard of the surficial coal deposit.

Jan 1, 1965

Jan 1, 1965

By G. Rowan, M. W. Clegg

Approximate analytical solutions for non-Darcy radial gas flow are derived for bounded and infinite reservoirs producing at either constant rate or constant pressure. These analytical solutions are compared with published results for non-Darcy flow obtained on digital and analogue computers, and the agreement is show to be very good. Some observations on the interpretation of gas well tests are made. INTRODUCTION The flow of gases in porous media is a problem that has been the subject of much study in recent years [l - 71 , and many methods have been proposed for solving the non-linear equations associated with it. The assumption that the flow satisfies Darcy&apos;s Law It has been observed, however, that the linear relationship between the flow rate and pressure gradient is only approximately valid even at low flow rates, and that as the flow rate increases the deviations from linearity also increase. It has been suggested by a number of authors that Darcy&apos;s Law should be replaced by a quadratic flow law of the form This form of equation was first suggested by Forchheimer [9] and, later, Katz and Cornell [10], and Irmay [lll, developed a similar equation. Houpeurt [12] derived this form of equation using the concept of an idealised pore system in which each channel consists of sequences of truncated cones giving rise to successive restrictive orifices along the channel. This type of representation leads to a quadratic flow law of type [4], for all fluids, but it is found that the quadratic term is only significant in the case of gas flow. The methods of Houpeurt for solving gas flow problems will be discussed further in another section of this paper. Solutions of the non-linear equation for Darcy gas flow 121 may be classified as either computer (digital and analogue), or approximate analytical ones. The former include the well-known solutions of Bruce et al. [13], and Aronofsky and Jenkins [14] , but the latter solutions, apart from the simple linearisation of equation (2) to yield a diffusion equation in p2 , are not so well-known. Amongst these approximate analytical solutions should be mentioned the work of Barenblatt [IS], who has applied the techniques of dimensional analysis to obtain similarity solution to a large class of non-linear equations; also, a number of Russian authors, including Barenblatt [16] , Kim [17] and others, who have used the method of moments for obtain-

Jan 1, 1965

By Wilbur I. Duvall

A linear array of shot and gage holes 30 feet deep in a granite outcrop was used to compare the size and shape of radial strain pulses produced in the rock when short cylindrical charges of cast composition B were detonated axially or at one end. The axially detonated charges produced radial strain pulses that had shorter rise times and larger peak strain than the strain pulses produced by end detonated charges.

Jan 1, 1965

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral&apos;iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,&apos; while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe&apos;s formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade&apos;s exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By R. L. Stegman, M. R. Achter

R. L. Stegman and M. R. Achter (U.S. Naval Research Laboratory)—In a study of the surface structures developed in the fatigue of nickel at low strains as a function of temperature, we have obtained similar results.3 As our apparatus permits fatigue tests to be conducted in vacuo, there was no masking of the surface at high temperatures by oxidation so that the structures there could be observed directly. The relatively few broad slip bands observed at room temperature gave way at 300°C to a large number of uniformly distributed and narrower slip bands. At 550°C deformation began to concentrate around the grain boundaries and progressively increased up to 800°C. In addition fatigue strength was observed initially to increase with increasing temperature up to about 600°C due to the effectively increased ductility caused by the dispersal of fatigue damage. The fatigue strength then decreased at higher temperatures as grain boundary cracking dominates. Maria Ronay, W. H. Reimann, and W. A. Wood (authors&apos; reply)— The authors are pleased to note that R. L. Stegman and M. R. Achter reach similar conclusions from their study of surface slip on nickel. However, they would emphasize that their own conclusions are based on what is shown by study of specimens that have been sectioned and that this study also shows that surface slip is not necessarily representative of what happens below the surface.

Jan 1, 1965

By R. E. Pray, M. C. Fuerstenau, J. D. Miller, B. F. Perinne

Quartz cannot be floated with potassium amyl xanthate as collector at any pH. Complete flotation is achieved with certain minimal additions of amyl xanthate and Pb from pH 5.8 to 8.5 and with amyl xanthate and Zn from pH 7.5 to 8.1. The active species of these metal ions responsible for activation are shown to be PbOH and ZnOH No flotation was effected when Cu and Mg were added as activators. Previous work1,2,3,4,5,6,7 has shown that quartz may be floated in the presence of sulfonate or soap when the following two criteria are met: 1) some portion of the added metal ion has hydro-lyzed to its first hydroxy complex, and 2) a precipitate of the metal-collector has formed. Since sulfonate and soap, two substantially different anionic collectors, conform to these criteria, this phenomenon may well be expected to be of a general nature. In this view then, it would appear that any anionic collector, including xanthates, should also float quartz when these two criteria are met. The object of this paper is to demonstrate the conditions under which quartz will respond to flotation in the presence of potassium amyl xanthate. EXPERIMENTAL MATERIALS AND TECHNIQUES Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Potassium amyl xanthate was selected as collector. Purification of this reagent was effected with the following method: 1) a laboratory sample of potassium amyl xanthate was dissolved to saturation in hot ethyl alcohol and filtered several times while still hot, 2) the filtrate was cooled, during which time potassium amyl xanthate crystallized out of solution; the xanthate was then separated from the solution by filtration, 3) the amyl xanthate was dissolved in fresh hot ethyl alcohol and filtered, 4) step (2) was repeated, 5) the crystalline potassium amyl xanthate was washed with ethyl ether five times, and 6) the xanthate was dried for 24 hours under continuous vacuum. Inorganic impurities are insoluble in hot ethyl alcohol whereas dixanthogen is soluble in ethyl ether. Five-gram charges of 48x150 mesh quartz were conditioned for 3 min in 125 cc of solution containing the reagents and were floated with the small-scale cell and procedure described in previous papers.478 Reagent grade HCl and NaOH were used for pH adjustment, while reagent n-amyl alcohol was added as frother. Frother addition is necessary with this technique, but it should be mentioned that data, similar to those shown in Fig. 2 for 1 x10-4 mole per liter Pb++ and 1 X 10-4 mole per liter AX-, were also obtained with a Hallimond cell in the absence of frother. EXPERIMENTAL RESULTS Clean quartz could not be floated with amyl xanthate at any pH. Flotation was achieved under certain conditions, however, when various metal ions were added to the system. The activating ions used were lead, zinc, copper and magnesium, added as reagent grade chloride salts. Lead as Activator: The effect of Pb++ as activator was examined at five different additions of amyl xanthate (Fig. 1, 2 and 3). When 1x 10-5 mole per liter xanthate was added in the presence of 1 x 10"4 mole per liter Pb ++, no flotation was obtained at pH 6.5 or below, while a recovery of about 60% was effected at pH 7. When the pH was increased to 7.8, no flotation was again obtained, Complete depression was noted from pH 7.8 to about 10, at which point a recovery of about 30% was achieved. At about pH 11, the precipitate of lead amyl xanthate which was present below this pH dissolved and complete depression occurred. When 2.5x 10-5 mole per liter xanthate was added with the same lead addition, no flotation was obtained at pH 5.8 and below, whereas a recovery of

Jan 1, 1965

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor&apos;s original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By B. A. Wilcox, A. H. Clauer

DURING the course of an investigation on the high-temperature creep behavior of TD Nickel* (Ni + 2) vol pct ThO2), it was observed that the creep fractures were similar in appearance to low-temperature ductile fibrous fractures and creep ruptures by cavitation. Microfractographs of fibrous ruptures are typically characterized by a dimpled appearance, with second-phase particles frequently found near the bottom of the dimples.&apos;-4 These somewhat resemble creep ruptures by cavitation, in that fracture occurs by void formation, with the subsequent growth and final merging of the voids to form a complete fracture.&apos; It is the purpose of this communication to describe the creep fracture of TD nickel and suggest a mechanism for the rupturing process. The discussion is relevant to material crept to fracture in vacuo at a constant stress of 18,000 psi, over the temperature range 900" to ll00°C. The material used in this investigation was 1/2-in.-diam bar stock supplied by Du Pont, contain- ing 2.3 vol pct Tho2. The final fabrication treatment consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fibered structure with a transverse grain size of -1 µ and a longitudinal grain size of 10 to 15 µ. Selected-area diffraction indicated that the fiber axis was parallel to (00l), in agreement with the results of Inman et a1.6 The thoria particle size varied from 80 to 1000Å, with an average size of 400Å, and the mean particle spacing was about 1200Å. The remarkable structural stability7 was confirmed by annealing for 6 hr at 1300°C (about &apos; 0.9 the absolute melting point). Transmission electron microscopy revealed that the only structural change was a slight decrease in dislocation density. Furthermore, recrystallization or grain growth during creep has not been observed. All specimens were annealed in vacuo at 1300°C for 3 hr prior to creep testing. The following times to rupture were obtained for vacuum creep tests at a constant stress of 18,000 psi: 900°C, 854 hr; 930°C,

Jan 1, 1965