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By C. H. Li, R. J. Stokes, T. L. Johnson

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.'," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By V. B. Kurfman

The temperature, strain rate, and orientation deDendence of defbrnzation of single-crystal MgAg has been examined. The crystals exhibit a tendency to single glide and little or no hardening at 25°C for many orientations. A much higher hardening rate is observed when multiple glide occurs, such as can be initiated by surface defects. The tendency for easy glide becomes less dependent on surface preparation and orientation as T — 100°C and bars so tested often fail after one-dimensional necking-. At T > 200°C (transition temperature for single-crystal notch sensitivity and poly crystalline ductility) single glide diminishes and two-dirnensionul necking begins. The crystals do not strictly obey a critical resolved shear stress law, but show the influence of {loo) cracks in determining the slip mode. The results are correlated with the difficulty of sciperdzslocation intersection and semibrittle behavior of this compound in single-crystal and poly crystalline form. Comparisons are made with the slip selection mode observed in tungsten, with the reported observations of easy glide in bee metals. and with the mechanical behavior of poly crystalline MgAg. PREVIOUS work on tensile deformation of polycrys-talline MgAgl and bending deformation of single-crystal MgAg2 has shown that the compound is semi-brittle (i.e., notch and grain boundary brittle). If this semibrittleness is supposed to result from the difficulty of multiple glide (associated with the problems of superdislocation intersection) one might expect single crystals deformed in tension to show pronounced single glide and strong orientation dependence of hardening rate. These experiments were done to examine this supposition and to study the tensile deformation of a highly ordered system which may be considered bcc if the difference between the two kinds of atoms is ignored (actual structure: CsC1). EXPERIMENTAL Single-crystal ingots were grown by directional freezing as previously described.&apos; These ingots were sliced into a by a by 2 in, rectangular bars by electric discharge machining, then round tensile bars were conventionally machined to 1/8-in.-diam by 1-in.-long reduced section. The bars were typically tested without an anneal because of the problem of magnesium vapor loss and they were typically tested as mechanically polished. The analyses are within the same limits as those reported earlier; i.e., the average composition for each specimen is within 0.5 at. pct of stoichiometry, while the total range from end to end in a given specimen varies from 0.7 to 1.4 at, pct. There has been no indication in the results of any variation in slip or fracture mode attributable to the composition fluctuations. The slip systems were determined by two-surface analysis of the bars after testing to failure at room temperature. Single glide was so dominant that there was little difficulty in identification of the dominant slip system even though the tensile elongation to failure often approached 7 to 8 pct in room-tempera- ture tests. Elevated-temperature testing was done in a silicone oil bath and low-temperature testing was done in liquid Np or a dry-ice bath. All stress measurements are reported as engineering stress unless otherwise specified, and crosshead travel is used as the strain measurement. RESULTS The tendency toward single glide is best seen in the pictures, Figs. 1, 2, and 3, which depict deformation at fracture as a function of test temperature. While it is possible to find regions of secondary slip by careful microscopy, such regions are very small. The development of a ribbon-shaped configuration from an initially round section bar pulled at 100°C is typical, occurred by single glide, and illustrates the degree to which such glide continues. At temperatures =100°C the bars typically show elongation of 20 to 50 pct by predominently single glide. Despite the large elongation, fracture even at 150°C occurs in a brittle mode, Fig. 2, in the sense that it is an abrupt failure which shows no discernible necking in the second dimension of the bar&apos;s cross section (i.e., there is no appreciable action of any slip modes which would decrease the broad dimension of the cross section). Near 200°C the fracture mode changes slightly. Although most of the sample extension is by single glide, after the bar develops the characteristic ribbon shape it begins to neck in the second (i.e., broad) cross-sectional dimension. The bar becomes very thin in the "necked down" region, Fig. 3, and the reduction in area approaches 100 pct. Often there oc-

Jan 1, 1967

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.&apos; When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.&apos;4-&apos;7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub&apos;s data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.&apos; Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200&apos; and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world&apos;s largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world&apos;s foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920&apos;s, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,&apos; published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By J. S. Rinehart, W. C. Maurer

The mechanics of impact crater formation in rock, particularly sandstone, has been sutdied, the velocity range being approximately that normally associated with oilwell gun perforators. The bullets were small steel spheres having diameters of 3/16, 9/32 and 7/16 in; impact velocities ranged from 300 to 7,000 ft/sec. The craters have two distinct parts — a cylindrical hole (or burrow) with a diameter the same as that of the impacting sphere, and a wide-angle cup comprising most of the volume of the crater. The burrow is fornred as material in front of the projectile is crushed and pushed aside, forming a cylindrical hole surrounded by a high-density zone. The clip forms as fractures are initiated in front of the projectile and propagate along logarithmic spirals, approximaling maximum shear trajectories, to the free surface of the rock. A most significant observation (made for the first time) was that, below the base of the cup in one type of sandstone, there are a group of similar fractures, not extending to the surface, which are spaced uniformly a few millimeters apart. Each fracture follows roughly the contour of the base of the cup and appears to require a certain threshold impulse to initiate it. These fractures comprise a relatively high fraction of the total, newly exposed surface area. The volume of the material removed by crushing varies as the first power of the impact velocity and the volume removed by fracturing, as the second power of the impact velocity. Penetration varies linearly with the impact velocity and is inversely proportional to the specific acoustic resistance of the target material, the proportionality constant being dependent upon the shape of the projectile. INTRODUCTION Yield of oil from a producing well is frequently enhanced by firing bullets and shaped charges through the well casing into the oil-bearing rock, forming craters and fractures from which oil can flow more readily. The purpose of this investigation has been to develop a better understanding of the mechanics of impact crater formation in rock, particularly sandstone, the velocity range being approximately that normally associated with oilwell gun perforators. FORCES OPERATIVE DURING IMPACT When a projectile moving at considerable velocity strikes a- massive target such as oil-bearing sandstone, intense and complex transient stress situations develop within both the projectile and the rock or sandstone against which it is striking. Usually the struck rock fails, the missile or projectile penetrating into the rock to some depth where it comes to rest or is forcibly ejected from its burrow by expansion of a plug of target material compressed in front of it. When the impact velocity is very high, the projectile itself may fail, breaking apart or becoming distorted; this situation is not considered here, the discussion being limited to nondeforming projectiles. Many experimental studies&apos;.&apos; have been carried out to determine the nature of the mechanics of crater formation and the salient features of the forces coming into play, some of the earliest studies being the French Army experiments performed at Metz between 1835 and 1845.&apos; The stratagem in most instances has been to make a post-mortem examination of the crater, measuring volume and depth of penetration and deducing force relationships from these observations rather than performing the more difficult (usually almost impossible) feat of measuring stresses during penetration. In many materials, the force acting during penetration of the projectile is found to be the sum of two components—(1) a constant force, independent of the velocity, representing some inherent strength of the target material; and (2) a component, proportional to the square of the velocity, representing inertial forces. For such materials, the average force per unit area acting on the projectile at any instant while it is in motion and being decelerated may be written F/A = a + bv2 . . . (1) where v is the velocity of the projectile at that instant, A is the cross-sectional area of the penetrating projectile taken normal to its trajectory, and a and b are constants which are dependent upon the target material and the shape of the projectile. It follows that the total penetration s is given by .........(2) where v, is the velocity of the projectile when it just strikes the target. Values of a and b for spherical projectiles impacting in a loose sand-gravel mixture and compacted earth were obtained in the Metz experiments. For sand-gravel, a and b are 620 psi and 0.0115 (psi) (ft/sec)&apos;, respectively; and for compacted earthworks, a and b are 432 psi and 0.0008 (psi) (ft/sec)&apos;. Figs 1 and 2

By George B. Clark

Many basic engineering principles of all four phases of mining operations, namely, prospecting, exploration, development, and exploitation, can be analyzed better in terms of quantitative geology. Geological data from both field and laboratory will also complement scientific methods now being developed. THE geological data emphasized so successfully in prospecting for new deposits, that is, structural controls, strength of solutions, and type of mineralization, are basically those required for successful exploitation. In the mining of newly discovered deposits the most economical methods should be employed as early as possible to keep the overall cost per unit produced at a minimum and to permit maximum extraction of valuable minerals. A crucial question is: How can geological data be translated into useful quantitative results which will aid in achieving this end? H. E. McKinistry&apos; has suggested that a solution may be reached in one of two ways: 1—the usual approach, use of judgment based on experience; or 2—mathematical calculations and tests on models, both subject to certain limitations. He also suggests that in addition to better use of geology more case data and theoretical data are needed on which to base sound judgment. Further research, therefore, is necessary. Perhaps in this field the emphasis should be on more specialization in mining methods and ground movement by men with thorough training in physics, engineering, geology, and underground mining. These specialists would be equipped to point out the most economical and scientific methods of exploitation. Selection of a stoping method is governed by the amount and type of support a deposit will require in the process of being mined, or by the possibility of employing the structure of the deposit to advantage in mining the ore by a caving method. In addition to these factors there are others which almost invariably influence the choice of an economical method of mining:&apos; 1—strength of ore and wall rocks; 2—shape, horizontal area, volume, and regularity of the boundaries of the orebody, and thickness, dip and/or pitch of the deposit and individual ore shoots; 3—grade, distribution of minerals, and continuity of the ore within the boundaries of the deposit; 4—depth below surface and nature of the capping or overburden: and 5—position of the de- posit relative to surface improvements, drainage, and other mine openings. In the final analysis it is usually necessary to disregard the less important of these factors to satisfy the requirements of the more important. Because of the variation of geological conditions throughout and surrounding the deposit, no mining method will be everywhere ideally applicable to the conditions encountered in one ore deposit. The immediate problem is to interpret the above physical characteristics of deposits in terms of geological characteristics. Very few quantitative geological data are available on the factors related to a choice of mining methods. However, there are many descriptive data in mining and geological literature which collectively show how important an effect details of geology have upon all phases of mining operations. The following categories of basic mining methods were investigated to establish the geological factors that have affected their successful application: 1— open stopes with pillars; 2—sublevel stoping; 3— shrinkage stoping; 4—cut-and-fill stoping; 5— square-set mining; 6—top slicing and sublevel caving; and 7—block caving. It should be noted that the first five of these methods are listed in the order of increasing support requirements. Mines were selected as examples only where geological descriptions were complete enough to warrant their use. A study of the geological factors involved in mining operations led to a choice of the following classifications, employed in Table I: 1—structural type of orebody; 2—dimensions (geometry); 3— country rock (type); 4—faulting, folding, and fracturing; 5—alteration of ore and rock; 6—type of mineralization; and 7—geological factors determining mining method (summary). Of these factors only one yielded results that can be defined from available data in a quantitative manner, i.e., dimensions of the deposit. These are the most reliable guides that can be used in selection of suitable mining methods. They are, in general, the properties of geologic structure most difficult to evaluate by studies of models, pho-toelastic studies, and other laboratory methods, all of which are at present more limited in their applications than the geologic method. Application of geology has proved a reliable guide in other phases

Jan 1, 1955

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal&apos; and by Chew and Connally&apos; for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7&apos; API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.&apos; All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By Robert W. Hendricks, John B. Newkirk

A simple method is described for determining the orientation of a single crystal by means of a cylindr cal X-ray camera. Orientation setting to within ±1 deg is attainable by a stereographic analysis of a single cylindrical Laue pattern produced by the originally randomly mounted crystal. Final precision adjustments which permit orientation of the crystal to within ±5 min of arc from the desired position can be made by the method of Weisz and Cole. A chart, originally Presented by Schiebold and schneider7 and which allows a direct reading of the two stereographic polar coordinates of the corresponding pole of a given Laue spot, has been recomputed to aid in the stereographic interpretation of the cylindrical Laue X-ray photograph. Detailed instructions for the use of the chart, a simple example, and a comparison with the conventional flat-film Laue Methods, are presented. 1 HE problem of determining the orientation of the unit cell of a single crystal relative to a set of fixed external reference coordinates is fundamental to most problems of X-ray crystallography and to many experimental studies of the structure-sensitive physical properties of crystalline materials. Several techniques for measuring these orientation relations have been developed which correlate optically observable, orientation-dependent physical properties to the unit cell. Examples of such procedures include the observation of cleavage faces or birefringence, as discussed by bunn,1 or the examination of preferentially formed etch-pits, as discussed by barrett.2 Each of these methods is limited, for various reasons, to an orientation accuracy of approximately ±1 deg—a serious limitation in some experimental studies. Several other limitations decrease the generality of these methods. Of these, perhaps most notable is the absence in many crystals of the physical property necessary for the orientation technique. The most widely used methods for determining crystal orientation are variations of the Laue X-ray diffraction method. Because of the indeterminacy of the X-ray wavelength diffracted to a given spot, the interpretation of Laue photographs is now limited almost exclusively to the procedure of using a chart to determine the angular coordinates of the corresponding pole for each spot. For the flat-film geometries, either a leonhardt3 or a Dunn-Martin4 chart is used in interpreting transmission patterns, whereas a greninger5 chart is used for interpreting back-reflection patterns. A less common method of interpreting flat-film transmission Laue photographs is by comparing the Laue pattern with the Majima and Togino standards,6 or with the revised standards prepared by Dunn and Martin.4 Although this last method is applicable only to crystals with cubic symmetry, it can be very rapid and just as accurate as the graphical methods. The primary limitation of all the X-ray methods mentioned is the relatively small number of Laue spots and zones which are recorded on the flat film. Often, few, if any, major poles appear, thus making interpretation tedious and sometimes uncertain. The use of a cylindrical film eliminates this problem. Schiebold and schneider7 prepared a chart by which the orientation of the specimen crystal could be determined from a cylindrical Laue photograph. However, it was only drawn in 5-deg intervals of each of the two angular variables used to identify the Laue spots, thus limiting the accuracy of orientation to about ±3 deg. An examination of this chart indicated that if it were drawn in 2-deg intervals, crystal orientations to ±1 deg would be attainable. Subsequent use of the replotted chart has confirmed this accuracy. It is the purpose of this paper to describe the redevelopment and use of this chart, and to point out its advantages and limitations. I) CAMERA GEOMETRY AND CHART CALCULATIONS The geometry of the cylindrical camera with a related reference sphere is shown in Fig. 1. The X-ray beam BB&apos; pierces the film at the back-reflection hole B, strikes the crystal at 0, and the transmitted beam leaves the camera at the transmission hole T. One of the diffracted X-rays intersects the film at a Laue spot L. The normal OP to the diffracting plane bisects the angle BOL between the incident and diffracted X-ray beams. The point P on the reference sphere can be located uniquely by the two orthogonal motions 6 and 8 on the two great circles ENWS and BPQT respectively. Because the Bragg angle 8 (= 90 - < BOP) is always less than 90 deg, P always remains in the hemisphere BENWS. Therefore, if every possible pole P is to be recorded on the same stereographic projection, it is necessary that the projection reference point be at T with the projection plane tangent to the sphere at B.* The great

Jan 1, 1963

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400&apos; to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,&apos; in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886&apos;C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4&apos;5 dense patches or clusters of prismatic dislocation loops, planar arrays,4&apos;10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10&apos; life level the

Jan 1, 1969

By Eckhard Nembach

The phase diagram of the system Pb-In has been investigated between -27° and + 40°C, using nzainly X-ray dijfraction. In accordance with t her mo dynamic measurements by Heumann and Predel, a segregation occurs at low temperatures, though not in the form of a nziscibility gap. THE phase diagram of the system Pb-In has been the subject of extensive investigations,1&apos;1 but recently Heumann and prede13 concluded from their thermodynamic data that a new feature should occur below room temperature. These authors observed that the maximum values for the enthalpy and entropy of mixing, which occurred at a composition of 50 at. pct Pb, were +400 and —1.7 cal per g-atom deg, respectively. From this the authors estimated that a miscibility gap should occur below 30°C, centered at 50 at. pct Pb. Resistivity measurements seemed to support this view. These authors proposed the phase diagram outlined in Fig. 1. Three phases exist at 30°C: the tetragonal indium phase with c/a > 1, the tetragonal intermediate phase a, with c/a < 1, and the fcc lead phase. During an investigation of the superconducting properties of Pb-In alloys. it has been observed4 that aging a specimen with 50 at. pct Pb for 14 days at -18°C decreased the superconducting transition temperature about 0.13"K and tripled the transition width. In this paper, the results of an investigation of the Pb-In phase diagram in the temperature range from — 2T to +40°C are reported. Superconductivity and X-ray methods have been used. 1) SPECIMEN PREPARATION The materials were provided by the American Smelting and Refining Co. According to the manufacturer their purity was 99.999 pct. The weighed amounts of the constituents were sealed in quartz tubes under an atmosphere of 10 torr helium, mixed for 24 hr in a rocking furnace at 380°C, quenched in ice water, and homogenized at 20" to 30°C below the solidus line, established by Heumann and Predel. The annealing times were 144 hr for specimens containing Less than 30 at. pct Pb and 36 hr for the remainder. 2) SUPERCONDUCTIVITY EXPERIMENTS The specimens were quenched from the homogeniza-tion treatment into ice water and their superconducting transition temperatures T, measured. The procedure used has been described in Ref. 4. The transition was detected by the change of the mutual induc- tance of two coaxial coils containing the sample. T, was defined as the temperature at which 50 pct of the total change in inductance had occurred. The repro-ducibility with which T, could be measured was i0.002"K. Then the specimens with lead contents between 38 and 75 at. pct were aged for 7 days at temperatures between -30" and 40°C. If this treatment caused T, to change by more than 0.005"K or the width of the transition to increase by more than 0.002"K, it was concluded that the specimen had undergone a phase change and no longer consisted only of the fcc lead phase: as it did immediately after homogenizing. The result is shown in Fig. 2. From this one can estimate at what temperatures and concentrations phase changes occur. The X-ray measurements were based on these preliminary results. 3) X-RAY EXPERIMENTS Because of the softness of the material, relatively coarse powders. 75 p, had to be used, which were filed in a helium atmosphere from homogenized specimens. The powders were annealed at least 30 min at temperatures between 120" and 16OJC, depending on their concentration, and quenched in ice water. Then their X-ray patterns were taken at -178°C with a Picker diffractometer, model 3488K, and a cold stage. on which the specimen was in thermal contact with a liquid-nitrogen reservoir. In this way the following relation was established for the fcc lead phase: a = 4.697 + 0.00247C for 40 5 C 5 75 11 where n is the lattice constant (A) and C is the at. pct of lead. The coarseness of the powder made it impossible to use lines with 0 > 75 deg; therefore n was averaged from lines with 45 deg 5 0 5 75 deg. The results were reproducible to within i0.05 pct. Relation [I] is very similar to the one found by Heumann and Predel at room temperature. Following this, homogenized specimens with compositions between 15 and 56 at. pct Pb were aged for at least 10 days at temperatures between -27" and

Jan 1, 1970

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.&apos; The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.&apos; and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,&apos; or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969

By K. E. J. Rapperport, C. S. Hartley

The only slip system observed in zirconium crystals deformed at 77", 575", and 1075OK was (1010) [1210] with a critical resolved shear stress in tension of 1.0 kg per sq mm at 77°K; 0.2 kg per sq mm at 575 °K; and 0.02 kg per sq mm at 1075 OK. The active twin planes were {1012}, (1121}, (11221, and (11233) with varying temperature dependence. A detailed analysis for the slip direction using Laue spot asterism is appended. NeARLY all metals of the hexagonal close-packed structure exhibit basal slip, i. e.,(0002)<1120>- type slip. This is true of magnesium,&apos; zinc,&apos; cadmium,3 beryllium,4 titanium,= yttrium,6 and rhenium.Many of these such as titanium 5&apos;8-&apos;0beryllium,4&apos;" magnesium, and zinc13&apos;14 display other slip modes even at room temperature, and nearly all have been reported to slip on other systems under particular loading or temperature conditions of testing. As is shown in this paper, basal slip was not found at any of four test temperatures from 77" to 1075°K in hexagonal close-packed zirconium under the simple loading conditions of tension and compression, even though in one case the resolved shear stress on the inactive (0002) <llgO> system was twenty-five times higher than the critical resolved shear stress on the active (1010) [1210] system. This result is consistent with prior studies on the active deformation processes in zirconium deformed at room temperature. &apos;&apos;-I7 SPECIMEN PREPARATION A) Material—The zirconium used in this work was of two types: 1) as-deposited reactor grade crystal-bar, and 2) arc-melted and forged reactor grade crystal-bar. Typical chemical and spectrographic analyses of these materials as received, and after hydrogen removal and crystal growth are given in Ref. 17. Crystals of type 1) above have the letter prefix (A) and those of type 2) have the prefix (B) throughout this paper. B) Crystal Growth— he zirconium was machined into rectangular parallelepipeds about 0.2-in. scl in cross section and 2 in. iong. These were hand polished through 4/0 abrasive paper, electropolished, given a hydrogen removal anneal, and subjected to long-time anneals at 840 °C in vacuo to produce usable crystals.&apos;7 A second technique used to obtain large crystals was to cycle the samples two or three times between 1200" and 840°C, allowing them to remain at the higher temperature for about 4 hr and at the lower temperature for 5 days.17 These techniques yielded some grains which occupied the entire cross section of the bar and were as long as 3/4 in. C) Orientation Determination—After the growth of large crystals by thermal cycling, the samples were repolished with extreme care through 4/0 abrasive paper and electropolished. Metallographic examination after polishing showed the surfaces to be free of visible deformation traces. Standard Laue back-reflection X-ray techniques were used to find the crystallographic orientations of selected large grains with respect to a specimen face and edge. Fig. 1 shows the stereographic projections of the stress axes for the crystals used. The sharpness of the spots on the Laue photographs indicated that the crystals were of good quality. EXPERIMENTAL METHODS Nine crystals were deformed in tension at 77"K, nine in tension and five in compression at 300°K in previous tests,17 fifteen in tension at 575"K, and eleven in tension at 1075°K. All specimens were stressed by load increments. After a predetermined load was applied, the specimen was removed from the loading appratus and metallographically examined for deformation traces. An attempt was made to initially stress each bar so that some crystals slipped a small amount and others not at all. This was done to bracket the critical resolved shear stress. One bar of special orientation (B-11) was repolished and annealed at 1075°K for 1 hr after lower temperature deformation, before final deformation at 1075°K. In the other bars the loading by increments, followed by metallographic examination, was continued until the surface distortion would interfere with analysis, or until fracture. One example of a crystal pulled to fracture is shown in Fig. 2. This photograph shows a crystal (B-14C) which was pulled at 1075°K and failed by slip on two (10i0) planes. The approximate orientation of this crystal is illustrated in the figure. Specimens were deformed at 77°K in liquid nitrogen on a tensile machine using an insulated bucket with an internal hook to accept a clamped specimen.

Jan 1, 1961

By U. K. Custred, E. W. Long, V. R. Degner

In 1973, the United States production of marketable phosphate rock set a record in excess of 42 million tons. This production rate is expected to continue to increase, due to the growing international requirement for fertilizer, at a rate exceeding 5% per year well into 1977. One approach towards increasing plant production capacity to meet the growing demand is through large-capacity flotation cells, provided they achieve metallurgical performance comparable to existing smaller cells. A 9-month evaluation test program recently completed at the Haynsworth mine at Bradley, Fla., demonstrated the feasibility of achieving economically acceptable concentrate grade and recovery levels using large, high-capacity flotation cells. The composition of the feed to the Haynsworth beneficiation plant is a typical Florida pebble phosphate matrix composed of phosphorite pebbles ranging in size from approximately 1-1/2 in. down to 150 mesh and intimately associated with a mixture of clay and sand (essentially silica). The feed contains approximately 22 to 28% phosphate reporting as tricalcium phosphate, Ca3 (PO,) 2, or "bone phosphate of lime" (BPL). The flotation section utilizes the double-float procedure typical of Florida plants. The phosphate is first floated away from the silica in the rougher circuit, using crude fatty acid, ammonia, and fuel oil or kerosene. Rougher conditioning is accomplished at 60 to 70% pulp solids with sufficient ammonia added to raise the pH to 9 to 9.5. Following coarse and fine rougher flotation, the concentrate (overflow) streams are joined and conditioned (sulfuric acid cleaned and washed) prior to entering the cleaner circuit where an amine float (cationic reagent and kerosene added in the feed box; pH 7.3 to 7.8) is employed to float the silica. The feed to the coarse rougher circuit averages 29% +35 mesh while the fine rougher feed averages 10%+35 mesh. Primary attention was directed toward the large rougher cell performance (recovery and grade) on coarse feed during the Haynsworth evaluation program. Flotation Cell Test Program A row of three No. 120 size (300 cu ft) WEMCO flotation cells was installed in parallel with an existing air-cell row. The total installed volume of the large cell circuit was 900 cu ft and required a floor space of 306 sq ft. This compared to the air-cell total volume of 200 cu ft and 152 sq ft floor space. (Both floor areas include feed and tails hoppers but exclude walkways.) Fig. 1 is a schematic cross section of the large flotation cell showing the relative location of key mechanism elements. In operation, the rotor generates a fluid vortex extending up along the walls of the standpipe and creating a sufficient vacuum within its core to ingest air into the standpipe/rotor cavity through the air inlet duct. The ingested air mixes with the pulp, which has been recirculated through the false bottom and draft tube, in the rotor. Further mixing occurs as the air and pulp move radially outward from the rotor, finally passing through the disperser into the flotation cell. Flotation is accomplished outside the disperser, where phosphorite laden air bubbles rise and the remaining pulp recirculates down along the cell wall to the false bottom and draft tube. Large-flotation-cell performance is influenced by the ability of the mechanism to (1) circulate, or suspend, the solids in the pulp; (2) ingest air into the rotor cavity; and (3) mix the air and pulp effectively. The proper balance between pulp circulation and air ingestion is a key consideration in achieving good recovery in a course feed application. Large-flotation-cell pulp circulation and air transfer characteristics are significantly influenced by rotor speed and rotor submergence; therefore, these two operational parameters can be used to "optimize" a particular mill application. Fig. 2 maps the hydraulic performance of the WEMCO No. 120 size flotation cell. This map can be used to relate the cell operational parameters which influence metallurgical performance. At a given rotor speed, power intensity (i.e., pulp circulation) is seen to increase, and airflow decrease, as rotor submergence is increased. The inverse relation between power and airflow is due to the two-phase air-liquid mixture density reduction accompanying the increased airflow rate. For any fixed rotor submergence, the power intensity (i.e., fluid circulation) and airflow both increase as rotor speed is increased. The selection of these two mutually related operating conditions (i.e., rotor speed and submergence) was a key consideration in the Haynsworth evaluation program.

Jan 1, 1976