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By Jean A. Andre

In 1969 "Société des Mines et Fonderies de Zinc de la Vieille-Montagne" produced 221,000 tons zinc ingots and 22,000 tons zinc dust, thus rating highest on the world's zinc producer list. The Company's plant at Balen, Belgium, with an output of 135,000 tons electrolytic zinc is the most important one of this group; it is an integrated metallurgical zinc and lead unit with recovery of most by-products. The present paper describes the zinc production facilities. The roasting section includes four fluid bed roasters (total concentrates charged: 740 tpd) and two sulfuric acid having a corresponding capacity. Calcine is leached in a fully automated plant by a two-step continuous process. Leaching residues, mixed with lead furnace slag, are treated in a shaft furnace. The recovered zinc fume is leached separately. In the near future, the leaching residues are to be treated by a wet process, developed in the Company's own laboratories. Purification of solutions is accomplished in two steps: antimony and zinc dust are added in the first one, only zinc dust in the second one for removal of cadmium. Electrolysis cells are partly of a conventional type. A new type of cell configuration was put onstream in October, 1969, planned output 60,000 tpy. Main features of the new cell rooms are the fully automatic pulling, stripping and replacing of the jumbo-size cathodes (immersed area 2.6 m2). Zinc cathodes are remelted in induction furnaces followed by in-line automatic casting and stacking machines.

Jan 1, 1970

By Pervez Patel, Martin G. Frohberg, Demetrios Papamantellos

Model experiments were carried out on the mass transfer of iodine between n-hexane and a 4 2 X 10-3 M aqueous sodium hydroxide solution. The influence of mechanical stirring by means of small gas bubbles (ca. 0.01 ml in volume) on mass transfer was examined in independent experiments. The results were described with the help of the penetration theory and in the case of bubble stirring with the help of a mathematical model based on this theory. S LAG-METAL reactions, especially those in steel-making processes, often occur under conditions where gas is evolved in the form of bubbles that break through the slag-metal interface. It is known that stirring by means of bubbles increases the mass transfer coefficient, but there has been very little quantitative work done in this field. Because of the difficulties that attach to experimental work at high temperatures this study was confined to model experiments at room temperature. EXPERIMENTAL APPARATUS The transport of iodine from an n-hexane layer into a weak sodium hydroxide solution was studied a) with stirring by means of bubbles and b) with mechanical stirring. The apparatus for the experiments with bubbles consisted of the cell, two Dreschel bottles filled with hexane in order to saturate the nitrogen flow, one flow meter, and a nitrogen gas cylinder fitted with a fine-regulating valve. Fig. 1 shows the cell consisting of a glass cylinder 33 cm in height with an overall diameter of 7.5 cm embedded in a copper flange. The flange is connected to a Plexiglas plate and to the gas inlet. The Plexiglas plate has holes of 0.2 mm diam bored into it which are spaced 1 cm from each other. For the experiments with mechanical stirring the bottom of the cell was sealed off by a Plexiglas plate. The upper layer was stirred by means of a glass stir-rer and the bottom layer with the help of a magnetic stirrer in a counter rotatory direction. Both stirrer speeds could be varied continuously. EXPERIMENTAL PROCEDURE Iodine dissolves in n-hexane producing a stable violet color thus enabling the iodine concentration in

Jan 1, 1970

By G. J. W. Kor, F. D. Richardson

The sulfide capacities a1 1500°C of slags in the systern CaO + CaF, +Al2O3 have been measured by bringing samples into equilibrium with gas mixtures made from CO + CO2 + SO, + N2. The capacities are negligzble both JOY CaF, and CaF, + Al2O3 melts but when lime is present even at 20 wt pct capacilies as high as 30 x lom3 can be obtained. The results have yielded information concerning the liquidus at 1500°C and fluoride-oxide melts in general. The slags used in electroslag refining contain substantial amounts of calcium fluoride. Robinson and Grainger' report that good results can be obtained by using slags of the approximate composition 70 wt pct CaF2 + 30 pct Al2O3. It has also been reported2 that a mixture of 50 pct CaF2 + 30 pct A12O3 + 20 pct CaO makes a good slag for general use. In view of the fact that very low sulfur contents are claimed for ingots produced by the electroslag process. studies have been made of the sulfide capacities [c, = wt pct S (PO2/Ps2)1/2 at 1500°C. of slags consisting of pure calcium fluoride, and of its mixtures with lime and/or alumina. These studies have also provided information on the phase diagrams. The slags were brought into equilibrium with gas mixtures prepared from NZ + CO + CO2 + SO2. Because CaFz is volatile and also easily hydrolyzed. measurements were made of its loss in weight in various flowing gas mixtures. EXPERIMENTAL Procedure. The apparatus and procedure were the same as described previously. Both platinum and iridium crucibles were used (height and inner diameter about 1 cm), but those made from iridium were stronger and able to withstand a greater number of experiments. In each experiment two crucibles were set in an alumina support and 1 g of slag mixture was divided between them. The materials from each crucible were analyzed separately after being brought to equilibrium with the gas, and then quenched in the water-cooled end of the reaction tube. Materials. Alumina and lime were prepared as de-scribed previously.4 Calcium fluoride was obtained by igniting Analar calcium fluoride in a platinum boat at about 800°C in a stream of pure dry nitrogen: the product was cooled in a desiccator. The slags were produced from mixtures of the powdered constituents, these being melted together in the course of each equilibrium experiment. The sulfur analyses and the X-ray diffraction meas- urements on the solidified slags were made as described previously.4 From the latter it appears that the CaF2 contained less than 0.5 mol pct CaO. RESULTS Values of (ps2/po2) for the Gas Mixtures. The re-sults have been represented in terms of (ps, /Po,)"? for the various gas mixtures used. The va1;es of this function at 1500°C are listed in Table I: they were calculated from the data cited previously for calculations at 1350°C 4 Weight Losses with CaF, and CaF, + CaO. The re-sults of the weight loss measurements* at 1500°C for

Jan 1, 1970

By Klaus Emicke

The paper describes the lead refining process operated at Norddeutsche Affinerie (N.A.). Incoming materials are different grades of lead with varying percentages of impurities: Cu, Te, As, Sn, Sb, Bi, precious metals. The facilities are designed for charge-wise operation. After drossing, generally Te, As, Sn and Sb are removed substantially by the Harris Refining Process using fused NaOH. A certain selectivity during refining is achieved by controlled addition of NaNO3. Another refining step is decopperizing by means of elemental sulfur. Complete separation of Te, As, Sn and Sb is accomplished by chemical methods in a leaching plant. A Howard Press is used in the Parkes Process for desilverizing. After vacuum dezinking in kettle, Bi is removed, if required, by means of Ca and Mg. In an end refining step Ca, Mg and Zn are removed by having the lead melt treated with NaOH and NaN03. The refined lead as such, or in the form of special alloys, is cast by an ingot casting machine into 50-kg ingots. Zinc which is used as a precipitant in the Parkes Process is recovered by distillation from the high grade Ag-Zn-Pb crystals in Faber du Faur retorts while the Pb/Ag alloy is fed to the cupellation furnace. Ca and Mg are removed from the Ca-Mg-Bi crystals formed in the course of Bi removal, and the Bi-bearing lead is cast into anodes. The electrolytic lead refining facilities at N.A. are operated largely for the purpose of separating Pb and Bi. These facilities are also used particularly for the refining of Bi-bearing lead which had gone through the above process, but from which Bi has not been removed by Ca and Mg.

Jan 1, 1970

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

Jan 1, 1970

By C. C. Harris

The 3-parameter equation* was introduced1 as having the necessary form and flexibility for describing the major features of size distribution curves. Also, Eq. 1 was shown to contain most of the widely used 2-parameter equations as special cases. Special methods are necessary in order to determine the parameters of 3-parameter equations by graphical means. The procedure given previously required double graphical interpolation followed by regraphing the interpolated data. The theoretical basis of the method was a difference equation eliminating y. Several other methods for obtaining the parameters have been under development and one method appears to overcome the disadvantages of the earlier method and satisfies several procedural requirements. The points in favor of the new method as compared to the earlier method are as follows: 1. Estimation of the quality of fit is direct, and is in fact an essential part of the procedure. 2. The data is plotted directly without the necessity of interpolation from a graph. 3. The method makes use of Rosin-Rammler2 paper which because of expanded scaling in the coarse sizes leads to improved accuracy1 as compared with the log-log plot for the Gates3-Gaudin4-Schubann5 representation. 4. There is a gain over the earlier method in overall accuracy and in simplicity.

Jan 1, 1970

By Giovanni Barla, Stefan H. Boshkov

This paper examines the application of gelatin mixture models to the study of factors such as gravity effects, tectonic and residual stresses, anisotropy, physical nonlinearity, time-dependent behavior of the rock mass and connectedness of the geologic space. The technique of calibrating gelatin mixtures proposed by Richards and Mark in 1966 is applied to the particular problem considered. Similitude relationships between model and prototype are discussed with reference to the constitutive equations describing the physical behavior of the rock mass. The interaction between two openings in a linearly elastic medium, under conditions of plane strain, is used as an illustrative example with the view to describing the history of stress and deformation changes on the rock medium and lining around a slusher drift while undercuts are made in block caving. The prediction of the displacement, stress field and mode of fracture associated with a given rock structure, its initial stress field, and its physical properties is essential to rock mechanics and ground control. The basic approach is to assume the rock mass to behave as a continuous, homogeneous, and isotropic medium. The classical theory of elasticity is the simplest theory based on such a concept. Specification of the elastic constants, the initial state of stress in the ground, and the boundary conditions on stress and displacement allows one to predict stress and displacement within the body. Subsequently, provided that a criterion which governs rock fracture under various stress conditions has been established, a stability analysis of the rock structure can be performed. A natural extension of the present knowledge consists of removing some of the simplifying assumptions which characterize the analytical solutions based on the classical theory of elasticity. Complex geometry, the significance of tectonic and residual stresses, anisotropy, physical nonlinearity, time-dependent behavior of the rock mass and connectedness of the geologic space are some of the important factors which are neglected in the classical approach. A better insight into the real problem can be attained with either the finite element method of stress analysis or an experimental technique. The former has already been applied with success on several occasion 1-4 and is destined to render great service in the field of rock mechanics and ground control. The latter, which will be considered in this paper, has been used extensively in applications too numerous to be enumerated. Experimental technique involves either prototype testing, if the area to be studied is accessible, or model testing. Two- and three-dimensional photo-elastic analyses are very convenient means of obtaining the stress distribution in models of complex geometry. In general, such analyses are confined to studies of stress fields around openings which are sufficiently far removed from the surface boundary so that the stresses in their neighborhood are practically equal to those produced by an initial uniform stress field; i.e., so that gravitational effects are negligible. There are, however, many rock structures where these effects must be taken into account to attain a more realistic representation of the problem. Surface and near surface rock structures, systems of openings interacting with one another, and structural components loaded only by their own weight are some of the obvious examples. This paper was written to show how factors neglected in the usual analysis based on the classical theory of elasticity, can be taken into account when gelatin mixture models are used inconjunction with photoelastic methods. The interaction between two openings in a linearly elastic medium, under conditions of plane strain, is used as an illustrative example, with a view to describing the history of stress and deformation changes on the rock medium and lining around a slusher drift while undercuts are made in block caving. The birefringence of gelatin mixtures has been known for some time. A series of experiments were carried out by Rossi in 1910,5 but after that very

Jan 1, 1970

By Jan D. Miller

The application of computers to the control and study of mineral processing operations such as grinding, classification and flotation has created an interest in simulation studies of these operations with mathematical models. Evidence of this interest is confirmed by papers presented at the 1969 International Computer Application Symposium held concurrently with the Fall Meeting of the Society of Mining Engineers in Salt Lake City, September 17-19, 1969. Proceedings of this symposium, entitled A Decade of Digital Computing in the Mineral Industry. were edited by Alfred Weiss and published by SME. Two sections of this book are devoted to computer application and simulation of mineral processing operations. In the area of comminution, several papers were presented at the International Computer Symposium. The size-discretized batch grinding model was described, and its application to the simulation of batch grinding, locked-cycle grinding and closed circuit grinding were discussed1. Freeh, Horst and Kellner2 approached simulation using a steepest ascent parameter-fitting technique, while Schoner3 considered the dependence of the elements of the mill matrix and classifier matrix on operating conditions, especially the feed rate.

Jan 1, 1970

By M. J. Pool, with Appendix by Larry Kaufman, R. W. Krenzer

Thermodynmic properties of the Cu-Mn system have been deterrrzined in the temperature range 973" to 1273°K by measuring the vapor pressure of manganese in equilibrium with alloys of compositions varying from 0.13 to 0.91 rnole fraction manganese using the Knudsen effusion technique. Activities of manganese calculated from the measured vapor pressures show large positive deviations. Calculated heats and entropies of mixing are positive with a maximum occurring at approximately 0. 7 mole fraction manganese. ThE investigation of thermodynamic properties of binary systems involving transition metals is of considerable interest at the present time. The incomplete subvalency electron levels of transition metals lead to unusual behavior in some alloys, and considerable information can be obtained by determining the thermodynamic characteristics of these systems and relating the thermodynamic behavior to observed physical properties. The Cu-Mn system, shown in Fig. 1,' provides an example of an alloy system in which the determination of the equilibrium phase diagram and various physical properties has received considerable attention, but very little work has been done on measurement of the thermodynamic properties. Elemental copper and manganese have comparable electronegatives, atomic sizes, and cohesive energies, but differ in crystal structure. They form a continuous series of solid solutions only at high temperatures and the structure varies in a continuous manner from fcc at the copper-rich end to fct at the manganese-rich end.' The purpose of this investigation was to measure the vapor pressure of manganese over a series of Cu-Mn alloys and from these values determine the thermodynamic properties of the binary system. Vapor pressure measurements were made in the temperature range 973" to 1273"K, remaining within the solid-solution region for each alloy studied. EXPERIMENTAL PROCEDURE The relative thermodynamic properties of solid Cu-Mn alloys were determined from vapor pressure measurements by means of the Knudsen effusion tech- nique. Several discussions of the theory can be found in the literature. In the case of copper and manganese, it is assumed that manganese is the only component subliming, so the vapor pressure of manganese over the various alloys can be determined directly by measuring the weight loss of the effusion cell. This is a valid assumption since the vapor pressure of manganese is about four orders of magnitude higher than the vapor pressure of copper in the temperature region of interest. The vapor pressure of manganese over the alloys at any given temperature is then related to the weight loss of the effusion cell per unit area per unit time. An upper limit of 1.5 x 10"s has been measured for the ratio of polyatomic to monoatomic molecules for manganese vapor in equilibrium with solid manganese at 1180°K, so it was assumed that manganese vapor is monoatomic. The effusion cells, fabricated from high-purity alumina, are 26 mm high, 18 mm OD, and have a wall thickness of 1 mm. Three different sized holes of 2.03, 2.54, and 3.18 mm diam were drilled in the lids from the inside face to minimize chipping, and the lids were then slip-cast onto the cells to provide a gas-tight seal. Alumina was selected for this particular application both because of its resistance to thermal shock and reaction with manganese vapor. In the ideal case, the orifice of the effusion cell should have a knife edge so that effusion through the orifice

Jan 1, 1970

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony' states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By Norman Yarborough

Much has been written about the energy fuels including their standing with respect to reserves, their delivered Btu costs, their potential in the electrical generating market and their capabilities to meet a burgeoning demand. Yet, when all factors are placed in their proper perspective, the spiraling electrical energy market alone should guarantee each fuel a better than average market for the foreseeable future. In fact, a study made by the U.S. Federal Power Commission on the spare capacity utilities have on hand indicated that 39 of the 181 major utility systems had less than 10% reserves on hand at the end of 1969. Fuel supplies are critically low in some areas, especially in the Southeast, South Central and Midwest areas of the U.S. In other systems equipment shortages resulting from faulty equipment or delays in getting new equipment deliveries causes power failures during peak loads. In addition, lack of labor curtails the erection of some new facilities and prevents many other facilities from operating at capacity.

Jan 1, 1970

By H. B. Muller

Single stage autogenous grinding of run-of-mine ore was selected by Broken Hill South Ltd., parent Company of Cobar Mines Pty. Ltd. for the concentrator to treat 60,000 tons per four weekly period of copper and complex copper-lead-zinc sulphide ores from the C.S.A. Mine at Cobar, Australia. Ore is mined by mechanised horizontal cut-and-fill stoping and is prepared for grinding by crushing under- ground in a 60 in. x 48 in. jaw-crusher set at 5 in. closed side setting. The ore is reduced to 80% minus 76 microns in two parallel sections each of one 22 ft. dim. x 7 ft. long autogenous grinding mill, powered by a 1,250 H.P. motor, operating in closed circuit with a single stage 20 in. dim. cyclone. Broken Hill South's original concept of the concentrator required the maximum use of reliable instrumentation, centralised control, and the minimum of manning. To achieve this objective the control room, housing the process recorders, alarms, closed circuit television monitors and all the control equipment, overlooks the grinding and flotation sections, and the whole plant is serviced by a public address system. The grinding units and associated equipment are located in the open and are serviced with the aid of a mobile crane and a mobile hydraulically-operated liner lifting device.

Jan 1, 1970

By R. R. Hart, B. C. Wonsiewicz, G. Y. Chin

In recent years there has been increased miniaturization of electromechanical devices to keep pace with current trends toward smaller electronic components. A major problem facing the designer, however, is the higher stresses encountered by the material as a result of shorter springs. Hence an improvement in the elastic limit, as approximated by the 0.01 pct offset yield strength, would be highly desirable. An increase of 25 pct in the yield strength, for example, will permit a 20 pct reduction in both the length and thickness of a cantilever-type spring while maintaining the same compliance. One technique of improving the yield strength that has received little commercial attention is crystal-lographic texture strengthening.1,2 Texture strengthening is expected to be most beneficial in materials of hcp structure, but considerable gain can also be expected in cubic materials. A wire with a (111) fiber texture, for example, is expected to be 20 pct stronger than randomly oriented material, and 50 pct stronger than wire with a (100) fiber texture.293 For sheet specimens with a {110}(112) texture, characteristic of many heavily rolled fcc alloys, the (111) transverse direction is expected to be the maximum yield strength direction, about 20 pct higher than that in the (112) rolling direction.' In addition, the (111) direction is the direction of maximum modulus of elasticity for most cubic alloys. A large value of the elastic modulus could be desirable in designs where stiffer springs are required. To test the above idea, a 0.090 in. (-2.3 mm) thick commercial grade A (5 pct Sn) phosphor bronze sheet, a widely-used material for relay springs, was rolled from the spring-tempered condition (60.5 pct reduction) to various additional reductions up to a total reduction of 95 pct. Subsequently, additional material was obtained with a total thickness reduction of 97.3 pct Standard tensile specimens were prepared from the sheet material with the tensile axis parallel to and at 90 deg to the rolling direction. Tests were run on an Instron testing machine at a strain rate of about 0.050 min-l. Textures were determined by the use of the reflection pole-figure technique. Data were obtained using nickel-filtered CuKa radiation and with the aid of a Siemens pole figure goniometer. The X-ray pole figure studies show an incrzasing development of the texture toward the {110}(112) ideal

Jan 1, 1970

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young's modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970

By Bruce A. Kennedy

The place of the young engineer in the mining industry has been the subject of a large number of keynote addresses, magazine articles, and papers in the past year. One of the best of these was the keynote address given by Mr. J. C. Kinnear, Jr. at the Fifth Annual Intermountain Minerals Conference in Vail. Colorado. Mr. Kinnear presented as part of his address the statistics of a Canadian survey Instigated to find out why young engineers and geologists are leaving the mining industry. The results of the survey showed four main reasons for leaving: 1) insufficient money 2) slow promotion 3) lack of association with senior engineers, as well as insufficient opportunity to keep abreast of technological development 4) geographic isolation

Jan 1, 1970

By Freeman Bishop

The Bureau of Mines is working on a long-term program to completely revolutionize mining-to create a mine-systems technology that integrates the need to recover minerals at low cost under safe and healthful working conditions while protecting the environment. Everyone should be brought into the planning process preceding each new mining development, the Interior Department urges, and Assistant Secretary Hollis M. Dole seems determined to push this kind of systems approach with everything he can move.

Jan 1, 1970

Jan 1, 1970

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By E. Miller, N. Chou, K. Komarek

The solid solubilities of the compounds PbS, PbSe, and PbTe have been determined by equilibrating single crystals with two phase alloys. The solubilities were determined by measuring the Hall coefficient of the equilibrated samples. The observed maximum deviations from stoichiometry on the lead rich and the chalcogen-rich side of the phase fields were: at. pct excess Pb at pct excess S at 850°C; PbSe--4 x 10'" at. pct excess Pb at at. pct excess at 800°C; and PbTe-2.8 x 10 4 at. pct excess Pb at 780°C, 10"1 at. pct excess Te at 720°C. The previously developed theory of retrograde solubility has been expanded to include intrinsic disorder in the compounds, and the experimental results are in agreement with the theory. THE solid solubility limits of intermetallic semiconducting compounds are of considerable interest, since many of these compounds have potential use as thermoelements in thermoelectric devices, as infrared detectors, or in semiconductor devices. The solidus curves of a significant number of these compounds have been reported to be retrograde with the maximum solid solubility occurring between the eu-tectic and the maximum melting temperatures. In a previous paper,' equations were derived which permit calculation of the maximum solid solubility of an AB compound exhibiting retrograde solubility. Derivation of these equations was based on the assumption that the compound is a nondegenerate semiconductor at the temperature under consideration, that the defects were unassociated, and that the vibrational contribution to the entropy of the compound could be evaluated by the Einstein approximation. It was shown that at the temperature of the maximum solid solubility The entropy term ASS is composed of the entropy of formation of the solid stoichiometric compound (AS$)*, and the entropy due to deviations from stoichiometric composition which is the sum of a con-figurational term (aS*), a vibrational term (AS,), and an electronic term (AS,). In the previous paper the positional entropy was evaluated considering the con- N. CHOU, Member AIME, formerly Graduate Student, New York University, N. Y., is with IBM, Yorktown Heights, N. Y. K. L. KOMAREK, Member AIME, formerly with New York University, is Professor, Department of Inorganic Chemistry, University of Vienna, Vienna, Austria. E. MI LLER, Member AIME, formerly with New York University, is Associate Professor of Mechanical Engineering, California State College at Long Beach, Calif. The paper is based on a thesis submitted by N. CHOU to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science. tributions from defects arising from deviations from stoichiometric composition. The derivation is generalized in the appendix to include intrinsic disorder. The electronic entropy term is also recalculated in the appendix. Of the various semiconducting compounds, the solidus curves of Pbs,' and ~b~e,~ have been most extensively studied. The solidus of PbSe has also been determined, but the temperature of maximum solubility has not been accurately established.5129 The present investigation was undertaken to compare the experimental solid solubility data for these systems with the values predicted theoretically. Since the temperature and composition of the maximum solubility of PbSe has not been accurately determined, experimental emphasis was placed on determining the solidus curves for PbSe in the region of maximum solubility, although experiments were also performed on PbS and PbTe at several temperatures. X-ray diffraction studies were also made on carefully prepared powder samples of PbSe to determine the variation of lattice parameter with composition. EXPERIMENTAL PROCEDURE The procedure of Brebrick and Allgaier was employed for determining the solidus data. Monocrystal-

Jan 1, 1970