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By S. G. Epstein

Electromigration has been measured in dilute liquid alloys of lead in antimony and antimony in lead. In these alloys antimony migrates with the electron current; lead migrates in the opposite direction. These results, which contradict the mass criterion, were predicted by the electron drag model for electromigration in liquid alloys. The existing experimental data are shown to correlate with the difference in electrical resistivities of the alloy components. FOR many years investigators have attempted to relate observed electromigration phenomena in liquid alloys to the physical properties of the alloy components. The most successful correlation was found by Angus et' al.,1 who in 1959 proposed an empirical criterion for predicting the relative direction of motion of the components of a liquid alloy in an electric field: the component with the smallest atomic mass concentrates at the cathode. While this criterion is obeyed in nearly all the alloy systems which had been investigated, the physical basis for such an effect was not understood. It was also disturbing that the mass criterion predicted the wrong sign for the Haeffner effect; observations with pure liquid metals revealed that in every instance the lighter isotope was transported to the anode.2 Klemm3 explained these isotopic separations by suggesting that the lighter isotopes were more mobile and more easily carried to the anode with the electron stream. Additionally, several deviations from the mass criterion have been found in liquid alloys, notably involving transition metals such as chromium, nickel, palladium, and zirconium, which migrate to the anode in liquid bismuth.4'5 Recently, a model has been proposed6 in which electromigration in liquid alloys is attributed primarily to the interaction between the electron stream and the metal ions. In essence, this model predicts that the component with the greater electron-ion scattering cross section will be preferentially transported to the anode, displacing the other component to the cathode. The electrical resistivity of each pure component at its melting point is taken as the measure of its scattering cross section. This model was developed from the results of systematic studies with various solutes in liquid mercury,7'8 bismuth,9 and sodium.10 In every alloy, the component with the greater resistivity has centrates at the anode. Coincidentally, in every instance the component with the greater resistivity has also the greater mass, apparently satisfying the mass criterion. In order to differentiate between electron-ion coupling and atomic mass as the relevant physical prop- erty influencing electromigration, measurements were made with Pb-Sb alloys. Lead has an atomic mass nearly twice that of antimony, but lead has an electrical resistivity of 91 microhm-cm while antimony has a value of 113.5 microhm-cm at their respective melting points. The mass criterion predicts that in an alloy of the two antimony will concentrate at the cathode; the electron drag model predicts that antimony will concentrate at the anode. EXPERIMENTAL To conclusively determine the relative motion of lead and antimony in each other, solute electromigration was measured in dilute liquid alloys of antimony in lead and lead in antimony. Both starting materials were 99.999+ pct pure. The measurements were made with the same capillary-reservoir technique previously used for measuring electromigration in liquid bismuth alloys.11 Several changes in the experimental apparatus were necessary, however, to accommodate liquid antimony, which has a higher melting point than bismuth. The modified apparatus is depicted in Fig. 1. In each experiment four quartz capillaries were filled with the molten alloy. A direct current was passed through two of the capillaries; the electrode in one of these capillaries was made the cathode, and the electrode in the other was made the anode. The remaining two capillaries sampled the alloy in the reser-

Jan 1, 1969

By Ronald J. McGregor, Anton R. Hendriksz

INTRODUCTION The NIMCIX contactor was developed in the late sixties at the National Institute for Metallurgy in South Africa, for the main purpose of extracting uraniuy from relatively low-grade uranium solutions. ' The concept was sufficiently developed by 1974 to permit the operation of a 1500 litre per minute column to treat unclarified urgnium-bearing solution under industrial conditions. The plant operated so successfully that several large-scale units have subsequent18 teen constructed and are operating efficiently. ' Total resin consumption figures as210w as 3 per cent per annum have been reported, and the extraction efficiencies of the installations have been exceptionally good. All the solutions treated have been acidic in nature and in every case have been of such a nature as to significantly depress the maximum uranium loading on the resin beads. The chemical constituents of the leach solution fed to the loading column determines the ease with which the soluble uranium can be absorbed by an ion exchange resin. The concentration of competing ions and various resin foulants define the nature of the continuous ion exchange equipment required for efficient extraction performance. The basic NIMCIX concept is retained in these various alternate designs, but batch or continuous elution methods with fully automated or manual control systems may be selected for the different process solution conditions. BRIEF DESCRIPTION OF THE NIMCIX CONTACTOR The NIMCIX ion exchange column is a multi-stage fluidized bed contactor which is designed to permit a counter-current flow of solution and resin in order to maximize extraction efficiency. The flow o resin is periodic, based on the Cloete and Streat 5 principle of reverse flow. The basic operating cycle can be divided into five periods, as illustrated in Figure 1. For the purposes of describing the cycle, the loading column is considered; how- ever, a similar sequence may be applied to the operation of a NIMCIX continuous elution column. S'I'EP 1: During the forward flow period, Solution flows up through the column and fluidizes the resin contained in each stage. The uranium depleted solution overflows the upper flared-section of the column as the tail solution. Step 2: The flow of solution to the column is temporarily stopped and the resin is allowed to Settle onto the plates in the column. STEP 3: During the reverse flow period, a fixed volume of solution is drained from the column to the transfer vessel. This flow causes resin transfer to occur from stage to stage and also out of the bottom stage. At the end of this period, which expires when the low level switch (LS) is actuated, some of the resin is left in the conical section of the column and the pipe interconnecting the column and the vessel. STEP 4: The cone flush period ensures that all the resin left in the cone of the column and the pipe is transferred to the transfer vessel before forward flow commences. STEP 5: The loaded resin in the transfer vessel, which has been isolated from the column, can either be hydraulically transferred to the top of the elution column or eluted in the vessel before being transferred to the top of the loading column. The major advantages associated with the NIMCIX concept are: (i) Simple method of operation (ii) Contactor can readily be scaled up to large diameters. (iii) Because the resin does not pass through pumps or airlifts, and valves cannot be closed on resin beads at any time, the resin losses are exceptionally low. (iv) Operating costs are low. (v) Relatively few valves in the system. (vi) Stable operation is achieved over a wide range of feed rates and concentrations.

Jan 1, 1980

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: I—maintenance of metallurgical balance, 2—conservation of oxide ore, and 3—mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak—Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pct, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pct of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1953

By C. A. Fothergill

An improved blotter model is described which makes use of a plastic sheet as base for the blotter field and pins to represent the input wells. The model is simple to construct and adapt and is particularly useful for demonstration purposes. Operational details are given. INTRODUCTION The blotter model was first applied to the investigation of oilfield problems by Wyckoff, Botset and Mus-kat,' primarily in order to demonstrate the flood patterns which could be expected from various arrangements of input and output wells in waterflooding projects. In recent years the model has been largely superseded for analog studies by the potentiometric and electric analog models which are more refined and versatile, since they can simulate the form, and, in certain cases, permeability variations which it is not possible to do with the blotter model. However, the latter is still used for analog studies where the reservoir can be represented as being uniform in thickness and permeability, and where a visual record of the flood advance is required. Ramey andNabor,2 for example, have applied the model to the investigation of areal sweeps in oil recovery by in-situ combustion. Because of its limitations, the blotter model can be used in general for only very simple arrangements of input and output wells, but within these limitations it has a definite advantage over all other types, in that it provides a picture of the advancing flood using the simplest and most easily constructed apparatus, by contrast with the gelatin model, for example, which requires more elaborate equipment. Moreover, the experiments can be quickly repeated and modified if necessary, whereas considerable time is required to prepare a gel field, compared with that required for the preparation of sheets of conducting blotting paper. For these reasons the blotter model can be very useful for demonstration and teaching purposes, enabling the student to experiment for himself with different arrangements of input and output wells. A model has been constructed for this purpose which is simple to operate and adapt. The model (Fig. 1) consists of a base platform or box, approximately 12-in. square, on top of which are screwed three lathes of 1/2 -in. square section to form three sides of a square 6 in. in length. This forms the support for a sheet of Cobex, transparent plastic, thickness .003 in., on which is carried the blotting paper representing the field. The plastic is flexible and relatively soft, and can be attached to the support by cellulose tape so that it can be easily removed when required. The input wells are represented by brass drawing pins pressed through the plastic sheet from the underside until the points are just projecting through the top; these are connected in the circuit as shown in Fig. 2. The sheet of blotting paper of required shape and size is saturated with a solution of 0.2 n-potassium sulfate to which has been added a saturated alcohol solution of phenol-phthalein at a strength of 10 cc/liter of stock solution. The surplus water is removed and the blotting paper placed in position on the plastic sheet making contact with the drawing pins and the sheet (which is an insulator). The anode consists of a second sheet of blotting paper cut as shown and saturated with the same solution. This is suspended from a laboratory stand, being connected to the conducting wire by means of a crocodile clip and making contact with the horizontal blotting paper at the projecting point. This is the method used by Ramey and Nabor and which permits the hydroxyl ions or colored front to reach the anode. As shown in Fig. 2, the electrical voltage used is 220-v DC and a shunt is placed across the terminals to step down the voltage as required. Further adjustment can be made as necessary using a lamp board in series with the shunt to obtain the

Jan 1, 1958

By T. A. Read, M. W. Burkart

The crystal geometry of the cubic-tetragonal interface after partial transformation of an indium-thallium alloy single crystal is described and a general theory is presented. The effects of applied stresses on this transformation are interpreted and the latent heat of transformation is obtained from observations of transformation under stress. A DIFFUSIONLESS phase transformation between face-centered cubic and face-centered tetragonal structures has been reported for the indium-thallium system by Bowles, Barrett, and Guttman1, 2 The transformation takes place at approximately 105 "C at 18 atomic pct Tl and 25°C at 23 pct Tl. In their study, Bowles, Barrett, and Guttman used poly-crystalline samples whereas in the present study single crystals were used to eliminate the transformation constraints imposed by adjoining grains. The use of single crystals made possible a comprehensive study of the effect of stress on the transformation. In the course of the work, it was possible to formulate a new method of analyzing dif-fusionless transformations (presented in this paper) which permits calculation of the geometry of the interphase interface from a knowledge of the crystal structures of the initial and final phases. The specimens were prepared from chemically pure thallium and 99.97 pct In which were weighed out to produce 3 to 4 grams of alloy of the desired concentration. The metal was placed in clean fused silica tubing, then melted, degassed and sealed under vacuum. (To obtain single crystals, it was found that both degassing and extreme cleanliness were essential.) Single-crystal specimens were grown by a modified Bridgman technique.8 pecimens were removed from the tube by dissolving the quartz in concentrated hydrofluoric acid which attacks the specimen very slowly. The specimen then was polished mechanically to produce four flat surfaces, electropolished, and annealed at 140°C for 48 hr. The electropolishing solution used was that described by Bowles, Barrett, and Guttman and the polishing was carried out on both the high and low temperature phases of the alloy. The high temperature polishing was done at 110°C with a stainless steel cathode. Visual Observation of the Transformation in Single Crystals A visual study of the transformation was made on specimens which had been electropolished in the high temperature phase. The specimens were supported on the stage of a metallograph by an electrically heated holder which contained an opening for observing the specimen. Visual evidence of transformation was found in the presence of an interface which separated the two phases. The interface plane defines the boundary of the phase undergoing transformation and manifests itself by the sharp change in angle between the surface of the specimen and the incident light at the juncture of the two phases. On slow cooling, well-annealed specimens transformed from the face-centered cubic structure to the face-centered tetragonal structure by the motion of a single plane interface which traversed the specimen from one end to the other. Upon heating, the interface moved back in the reverse direction. The interface could be started, stopped, or reversed at will. A temperature hysteresis of about 31/2oC was observed in the reversal of the interface. Holding an interface stationary caused it to disappear completely in most cases, whereas in other instances the interface became less distinct depending upon its orientation. The interface could be made to reappear by changing the temperature of the specimen. The low temperature tetragonal structure exhibits only the fine markings or subbands reported by Bowles, Barrett, and Guttman and is illustrated in Fig. 1. These subbands are twin-related. Back-reflection Laue patterns show the breakup of the cubic spots into pairs of spots corresponding to the twin orientations of the tetragonal phase.

Jan 1, 1954

By G. Derge, R. E. Grace

Diffusivity of bismuth in liquid Pb-Bi alloys has been measured by the capillary reservoir method as a function of temperature and composition. Fair agreement between theory and experiment is found for the measured diffusion coefficients and activation energies of diffusivity and viscosity in dilute lead alloys. The measured diffusion coefficients in the high bismuth alloys describe mass transport in special concentration gradients. THE study of diffusion in liquid metals has been restricted largely to the amalgams over small ranges of temperature and composition. In contrast to this, diffusion and transport of ions and molecules in aqueous and organic solvents have been studied extensively for the past 50 years. The general difficulty of measuring diffusion coefficients in both gases and liquids at high temperatures has been that of eliminating convection currents. Measuring techniques based on freezing and sectioning after the diffusion period1 are not particularly satisfactory because of the volume changes and segregation which occur during freezing. The most promising technique which is currently being developed for liquid metals is the capillary reservoir method. This eliminates convection currents from the diffusion zone and requires measurements only of the length and initial and final compositions of the alloy within the capillary. Anderson and Saddington' have measured the diffusion coefficient of tungstate anions in aqueous Na,W04; Wane4' and Hoffman- ave studied structure and self-diffusion in water and self-diffusion in mercury, respectively, by similar techniques. Selection of the Pb-Bi system for initial study was made for several reasons: I—It afforded a low temperature system for development of techniques which would be suitable for high temperature measurements in liquid iron. This research on diffusion in liquid iron is now in progress as a part of a general program on the rates and mechanisms of slag-metal reactions. 2—Activity data on liquid Pb-Bi alloys of all compositions are available from the emf meas- urements of Strickler and Seltz.9 3—Some data are available on the diffusion of bismuth into solid lead. The measurements on solid alloys were made by von Hevesy and Seith7 for the concentration range of 0 to 2 pct Bi. An appropriate solution to Fick's law (unsteady state) for the capillary reservoir has been found by considering the mass flow which passes through a unit area of surface on a slab of infinite thickness as a function of time. This is the first application of this solution to diffusion measurements, although a similar solution is available for identical boundary conditions.' By analogy with heat conduction, the problem reduces to a perfectly insulated infinite slab at temperature C,, one surface of which is quenched to C, for all times, t. Heat is permitted to flow from quenched surface of the slab to an infinite supply of coolant at C.' (see Appendix). For the corresponding solution for diffusion in liquids, these terms become Where Cu is the initial concentration of component A" in entire capillary at t - 0, C, is the final con- In this case. component A is bismuth, and C, = 0. centration of component A in entire capillary at t = t, C, is the concentration of component A in bath for all t, 1 is the length of the capillary in centimeters, t is the time of diffusion period in seconds, and D is the diffusion coefficient in square centimeters per second. By comparison with solutions to Fick's law used in the solid state, this solution for liquids is similar to the Grube solution for solids, where the change in D with chemical composition is not taken into consideration. Difficulty is to be expected if large concentration gradients are employed and if the concentration gradients extend over an appreciable length of the capillary.

Jan 1, 1956

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: I—maintenance of metallurgical balance, 2—conservation of oxide ore, and 3—mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak—Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pct, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pct of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1953

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By T. M. Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the `active masses' of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. [ ] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, [ ] where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of unfloatable mineral. Hence the first order equation is [ ] It has been proposed by various workers1-3 that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris' has discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1952

By W. C. Lilliendahl, G. Meister

Uranium metal with a purity of about 99.9 pct was produced on a large scale by fused salt electrolysis with a material efficiency of about 90 pct. The material efficiency depends mainly on bath composition, electrolysis temperature, electrode smothering, and elutriation during washing of the powder. RESEARCH and development work on fused salt electrolysis carried on by the Westinghouse Lamp Div. Bloomfield, N. J., was done under the Manhattan District Corps of Engineers and later under the Atomic Energy Commission for the commercialization of uranium production for the first atomic pile at the University of Chicago in 1942. From the conception of the atomic bomb project it was recognized that metals with impurity levels having little metallurgical significance would be required. Permissible impurity levels were based on neutron absorption. Of particular significance was boron, which could not be present in amounts exceeding 1 ppm. The electrolytic method as developed in 1930 by Driggs and Lilliendahl,1,2 and later improved, yielded uranium of very low boron and other deleterious impurity content. No other method was capable at that time of producing uranium metal of the required purity.' The low boron content of uranium produced by the electrolytic process resulted from the availability of the reactants which were low in boron content, and from the inherent elimination of boron in the fused salt bath. Since the heart of any electrolytic process is the electrolysis cell, this paper will deal with the development of the original bath composition for the efficient production of uranium from a batch process to one of continuous operation. Emphasis also will be placed on other factors which will affect the material efficiency of the process. With the laboratory cell the material efficiency of uranium powder recovery in the early electrolysis was relatively low, about 35 pct based on the ratio of uranium recovered to uranium added. This early process also had other defects. The electro- lytic bath could not be used continuously. After three runs from a freshly charged crucible, the deposit showed a tendency to slip off the electrode as it was raised from the bath. This condition necessitated pouring the charge every fourth run and preparing a new bath. It was assumed at that time that this condition was caused by the increasing fluoride concentration with each addition of uranium salt, which adected the mobility of the uranium ions. Experimental The electrolysis cells differed in size only. They were of the floating cathode type. The laboratory cells were 21/2 in. ID and 6 in. deep and operated at 30 amp and 5 volts. Production was about 150 g metal powder per 8 hr. The plant cells (5 units) were 9 in. ID x 21 in. deep and operated at 1800 amp at 12 volts. The total production unit was designed to produce 250 lb of uranium powder per 8 hr day. Because of the tendency of uranium fines toward spontaneous combustion, material efficiencies were based only on the recovery of useful coarser metal which could be safely handled. The reported efficiencies are of particular significance only as related to the same group of experimental procedures. At the start of the project no changes were contemplated until previous data could be definitely confirmed. Therefore, the first experiments were with the 50 pct CaCl2-50 pct NaCl mixture. The material efficiency of uranium deposition as a function of the number of electrolyses is shown in Table I. In Table I, the decrease in efficiency at 800°C with number of runs is apparent and confirmed the earlier data. Operating at 900°C enabled the number of runs to be doubled, but before pouring the charge the efficiency of recovery became poor. This test indicated that the improved efficiency might have been caused by an increase in the fluidity of the bath.

Jan 1, 1958

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

A. Cook K.A. Grace's article advocates usage of the terms describing resources as defined by the US Bureau of Mines (USBM) and the US Geological Survey (USGS). Originally recommended in 1943, the terms were revised in 1976 and again in 1980. Mr. Grace further recommends that the term reserves should be severely restricted and that it should encompass mining and processing factors. The list of references quoted in the article does not, however, mention the study concerning reserves that was made over a period of almost four years by a joint Committee on Definitions. This committee was sponsored by three societies - the American Institute of Mining, Metallurgical, and Petroleum Engineers (AIME), the Society of Economic Geologists (SEG), and the American Institute of Professional Geologists (AIPG). Most of the detailed work was done by a working party appointed by the Society of Mining Engineers (SME) of AIME. After studying previous definitions in the US as well as in the United Kingdom, Canada, Australia, France, and other European countries, the following definitions were proposed and accepted in 1974 by the SME board of directors. (Ore reserve definitions in Rhodesia, South Africa, or New Zealand were not mentioned as having been reviewed. Table 1 lists definitions from MINING ENGINEERING, July 1975. Notice in Table 1 it was mentioned, under Resources, that the definitions of reserves were recommended for the purposes of commercial evaluation. It was further stated that the terminology adopted by the USBM and the USGS, as released to the public, covering resources, was recognized as such. Mr. Grace also recommends that reserve calculations should allow for future losses in ore tonnage, ore grade, milling, and smelting. Unfortunately, it might take years to develop a prospect after it has been discovered. Mining methods have to be tested before being finalized in order to know what tonnage of ore is going to be lost, or how much dilution is likely to occur. The same problems are present in concentrating or in smelting. Operating mines usually know how mined grade compares with ore reserve grade. They can usually predict fairly closely what their final metal recoveries are probably going to be. It is, however, expecting too much to have to delay quoting reserves from say a recently drilled prospect. Any responsible mining geologist or mining engineer (or company for that matter) should state several things about an ore reserve calculation: that it is or is not a preliminary estimate only; that estimated grades have not been diluted to allow for a future, as yet unknown, mining method; that metal recoveries are or are not only tentative, based perhaps on drill hole samples only or on no metallurgical testing at all. [ ] Reserves of a partially explored prospect are always quoted when it becomes necessary to raise capital. If they are described as preliminary only (really just tonnage and grade estimates and not true "reserves") in addition to being accompanied by some of the items just mentioned, nobody is going to be misled. If, on the other hand, a report by a member of the SME or SEG is intentionally misleading, the individual must be reported and eventually disbarred from his or her society. To summarize, let us stay with the definitions of ore, ore reserves, and related terms as recommended and accepted by SME. I might add that on occasion I have used a fourth category in my ore reserve calculations, namely Geologically Possible Ore. This category is more or less the same as Inferred ore defined by the USBM and USGS. I have never given a grade to this category, which may be based only on geological mapping, geochemical sampling, or geophysical traversing. ?

Jan 1, 1986

By Fredrick C. Pearson, Albert Brown, Emil R. Ermert

EARLY in 1946 the Shen-Penn Production CO., a subsidiary of the Philadelphia and Reading Coal and Iron Co., was organized to operate the Shenan-doah Stripping, one of the largest open-pit anthracite mines in the world. This mine is located in the Western Middle Field near Shenandoah, Schuylkill County, Pa., and involves the removal of approximately 60,400,000 cu yd of overburden to permit the recovery of 9,200,000 gross tons of rough cleaned coal from an area 8000 ft long and 2700 ft wide, with a maximum depth of 400 ft. Operations began in August 1946, and within the next few years 31,811,-000 cu yd of overburden and 2,994,000 gross tons of rough cleaned coal had been removed. During the early days of open-pit mining operations, steam was the primary motive power. However, as the size of the equipment increased, so did the problems of fuel, water, labor, and maintenance. Because of its efficiency and convenience, electric power rapidly replaced steam. Later the modern diesel engine was developed, and today practically all stripping equipment is either electric, diesel-electric, or diesel-powered. In locations where electric power is not readily available or where operations are scattered over a large area, diesel power is favored. At Shenandoah operations are highly concentrated in a relatively small area, and this fact, coupled with the availability of ample electric energy, indicated the selection of electric-powered equipment. Since this was a new company, it was necessary to purchase every item, from the smallest tools to stripping shovels. Although the organization period was hampered by the postwar scarcity of materials, an excellent opportunity was afforded to set up a thoroughly modern plant. This paper will describe the power facilities, with particular emphasis on the more unusual features. The substation is a major item in a power distribution system, and a simple arrangement utilizing high quality equipment is an excellent investment. With this in mind, a 3000-kva unit type substation was selected and installed. This unit is made up of three sections, which are assembled simply by bolting together the various sections and connecting the power leads, see Fig. 1. The transformer proper, rated at 3000 kva, is oil-filled and nitrogen-sealed, having a 66,000-v Delta primary and 4160-v Wye secondary with a grounded neutral and 46-ohm ground resistor. The function of this resistor will be described later. Electrical energy is purchased from a public utility and is delivered to the main substation at 66,000 v over one or the other of two incoming lines. These lines terminate on a high voltage switching section on which high voltage fuses and Thyrite lightning arresters are installed. The outgoing feeder switching unit is made up of the following: 1—An auxiliary compartment consisting of potential and current transformers with necessary terminal blocks for connecting to power company metering equipment. 2—Another auxiliary compartment containing a control transformer, battery, and battery charger for the furnishing of power for tripping and reclosing of power circuit breakers. The assemblies in these auxiliary compartments are mounted on carriages that can be rolled in and out with ease. Potential transformers are readily accessible for inspection and fuse replacement. When withdrawn from the operating position they are completely de-energized and grounded. 3—Two feeder breaker compartments, each with a 1200-amp, 5000-v, solenoid-operated magneblast air circuit breaker, voltmeter, ammeter, overcurrent relays, and a ground relay. These power circuit breakers can be quickly and safely withdrawn or repaired. A built-in isolating mechanism is used for lowering the breaker to a transfer truck for repair or inspection or as a means of disconnecting the breaker from the source of power as an added precaution when working on power lines. Thus inspec-

Jan 1, 1953

By Albert Brown, Emil R. Ermert, Fredrick C. Pearson

EARLY in 1946 the Shen-Penn Production CO., a subsidiary of the Philadelphia and Reading Coal and Iron Co., was organized to operate the Shenan-doah Stripping, one of the largest open-pit anthracite mines in the world. This mine is located in the Western Middle Field near Shenandoah, Schuylkill County, Pa., and involves the removal of approximately 60,400,000 cu yd of overburden to permit the recovery of 9,200,000 gross tons of rough cleaned coal from an area 8000 ft long and 2700 ft wide, with a maximum depth of 400 ft. Operations began in August 1946, and within the next few years 31,811,-000 cu yd of overburden and 2,994,000 gross tons of rough cleaned coal had been removed. During the early days of open-pit mining operations, steam was the primary motive power. However, as the size of the equipment increased, so did the problems of fuel, water, labor, and maintenance. Because of its efficiency and convenience, electric power rapidly replaced steam. Later the modern diesel engine was developed, and today practically all stripping equipment is either electric, diesel-electric, or diesel-powered. In locations where electric power is not readily available or where operations are scattered over a large area, diesel power is favored. At Shenandoah operations are highly concentrated in a relatively small area, and this fact, coupled with the availability of ample electric energy, indicated the selection of electric-powered equipment. Since this was a new company, it was necessary to purchase every item, from the smallest tools to stripping shovels. Although the organization period was hampered by the postwar scarcity of materials, an excellent opportunity was afforded to set up a thoroughly modern plant. This paper will describe the power facilities, with particular emphasis on the more unusual features. The substation is a major item in a power distribution system, and a simple arrangement utilizing high quality equipment is an excellent investment. With this in mind, a 3000-kva unit type substation was selected and installed. This unit is made up of three sections, which are assembled simply by bolting together the various sections and connecting the power leads, see Fig. 1. The transformer proper, rated at 3000 kva, is oil-filled and nitrogen-sealed, having a 66,000-v Delta primary and 4160-v Wye secondary with a grounded neutral and 46-ohm ground resistor. The function of this resistor will be described later. Electrical energy is purchased from a public utility and is delivered to the main substation at 66,000 v over one or the other of two incoming lines. These lines terminate on a high voltage switching section on which high voltage fuses and Thyrite lightning arresters are installed. The outgoing feeder switching unit is made up of the following: 1—An auxiliary compartment consisting of potential and current transformers with necessary terminal blocks for connecting to power company metering equipment. 2—Another auxiliary compartment containing a control transformer, battery, and battery charger for the furnishing of power for tripping and reclosing of power circuit breakers. The assemblies in these auxiliary compartments are mounted on carriages that can be rolled in and out with ease. Potential transformers are readily accessible for inspection and fuse replacement. When withdrawn from the operating position they are completely de-energized and grounded. 3—Two feeder breaker compartments, each with a 1200-amp, 5000-v, solenoid-operated magneblast air circuit breaker, voltmeter, ammeter, overcurrent relays, and a ground relay. These power circuit breakers can be quickly and safely withdrawn or repaired. A built-in isolating mechanism is used for lowering the breaker to a transfer truck for repair or inspection or as a means of disconnecting the breaker from the source of power as an added precaution when working on power lines. Thus inspec-

Jan 1, 1953

By C. A. Hope, H. B. Wishart

THE number and severity of surface imperfections on rolled slabs, assuming the reception of uniformly good quality heats from the open hearths, depend upon a number of conditions associated with heating and rolling of steel in the primary mills. While there are other elements that have an effect on surface quality, rather than make this paper too lengthy the discussion of mill processing variables will be limited to three factors in order to illustrate their effect on slab surface quality: 1—amount of reduction between ingot and slab, 2—slab finishing temperatures, and 3—influence of roll changes. Measurement of the percentage of surface removed by scarfing on the flat surfaces of the slabs was used for evaluating quality in this study. A study of this nature must be made on slabs that are inspected and conditioned under uniform conditions and standards. In order to be certain that steel of the best possible steelmaking quality was received at the rolling mills, a low carbon deep drawing grade of rimmed steel, made for sheet mill application and manufactured under carefully controlled open hearth practices, was selected. Use of this particular steel thereby reduced the steel quality factor as a possible source of variation. The measure of slab surface quality is the amount of surface removed by scarfing during yard conditioning and is expressed as percentage of surface removal. This percentage was estimated by experienced personnel to uniform standards and it should be noted that these percentage figures are representative only for the grade selected and under the rigid inspection standards to which the slabs were subjected. Surface removal is a matter of concern because the imperfections, if undetected, often are the cause of poor surface quality in the finished product and their removal, by conditioning, add to the total plant costs. The data was collected at various times over a period of six months and, with normal weekly fluctuation in the level of quality, it is to be expected that for any period of sampling there will be some variation in the plotted results. The type of defect that is responsible for most slab conditioning at Gary Steel Works is a light angular surface break. This defect is usually interconnected to form large defective areas and occurs mainly on the bottom half of the slab on both sides. This type of defect is illustrated in Fig. 1, showing a bottom portion of a slab; while a close-up of an area of the same slab where the surface breaks were found is given in Fig. 2. The large dark areas are heat patterns, results of hot stacking and cooling. Independent of these light breaks, but sometimes associated with them, are larger and deeper isolated breaks. However, most of the surface removal occurs from conditioning the large areas of small breaks. There are also occasional scabs of varying degrees of severity but these are relatively infrequent. The slabs are generally free of rolled-in scale. Ingot to Slab Reduction vs Quality Some ten years ago at Gary Steel Works, the minimum slab ingot thickness was 30 in. Subsequent operating and other quality features indicated the desirability of using an ingot of reduced thickness with the result that a series of molds that would produce a 22 in. thick ingot with various widths was adopted as standard. A minimum number of the thicker mold sets are still used. From the standpoint of quality difficulties from pipe and segregation, the smaller ingots are an improvement. From a quality surface viewpoint, the slab product from the thin molds requires approximately twice the surface removal as the slab product from the thick molds. This is shown in Fig. 3 where the percentage of surface removal is plotted against slab product rolled from

Jan 1, 1956

By M. J. Hordon

Measurements of the 103 yield stress of ordered and disordered poly crystalline Cu ,Au were related to the ordered antiphase domain size determined by resistivity measurements. For undeformed material, a yield stress maximum wa obtained at a critical domain diameter of about 40A. Plastic deformation resulted in a marked increase in the yield stress and electrical resistivity of the ordered alloy compared to the disordered, the strain hardening rate increasing regularly with initial antiphase domain size. Order hardening was accompanied by a sharp reduction in size of the initially large domains. It has been observed that the yield stress of ordered and partially ordered Cu3Au alloy varies sensitively with antiphase domain size aid degree of order.ly2 In addition, ordering of the lattice leads to a marked increase in the strain hardening rate (order hardening) as compared to the rate for the disordered alloy. In the present investigation, changes in the electrical resistivity and yield stress of ordered polycrystalline Cudu with varying initial domain diameters were measured after tensile plastic deformation in order to examine the effect of cold work on the antiphase domain size. EXPERIMENTAL PROCEDURE Au-Cu alloy of 99.99 pct purity analyzing 50.85 wt pct Au-balance copper was obtained from the Handy-Harmon Co., N. Y., in the form of 0.061 in. diam drawn wire. Wire specimens 3 in. in length were given the following annealing treatment in nitrogen: 500" for 72 hr, 820" for 15 hr, and 450" for 5 hr, followed by a water quench. The annealing sequence resulted in a completely disordered structure with a grain size of about 0.2 mm. The disordered specimens were then reannealed at 360' in nitrogen for periods varying from 10 min to 150 hr followed by quenching to produce ordered structures with varying domain sizes. The degree of ordering and variation of domain size was followed by electrical resistivity measurements made at room temperature using a low resistance precision Kelvin double bridge apparatus. The specimen resistance was determined over a length of 4.0 cm between two brass knife-edge contacts while the specimen was immersed in an oil bath to minimize temperature variations. In addition, the current flow in the circuit was minimized by a current pulse technique in balancing the bridge in order to avoid heating the specimen. Using a sensitive galvanometer to detect the bridge null, the accuracy of the resistance measurement Wire specimens were plastically strained in tension with an Instron tensile unit at strain rates in the range 5 x 10"5 sec-' to 2 x 10"4 sec-'. Stress and extension data were fed into the Instron chart drive amplifier to obtain the actual stress-elongation curve from which the yield stress at 10"3 strain was determined. The maximum resolution of the apparatus was approximately 50 psi stress and 3 x 104 strain. At various plastic strain levels, deformation was interrupted and the electrical resistivity determined after removing the stress. RESULTS AND DISCUSSION 1) Yield Strength of Ordered Cudu. In order to determine the effect of the ordered antiphase domains on the initial yield stress, specimens were prepared with varying domain sizes ranging from zero for 5 completely disordered structure to about lo5A for a completely ordered structure by suitable annealing treatment. Domain sizes were estimated by comparing room temperature electrical resistivity data with the original data of Jones and sykes3 as modified by rdle.' In agreement with previous work, the resistivity varied sensitively with domain diameter and degree of order, decreasing from approximately 11.6 x l0- ohm-cm for the disordered structure to about 5.9 x l0- ohm-cm for ordered domains above 10"3 cm in diameter. Fig. 1 shows the change of the 103 yield stress with ordered domain size. It is evident that the maximum

Jan 1, 1963

By Mason K. Banks

A process has been developed which produces spodumene concentrates assaying 6.0 pct Li2O and 0.45 pct Fe2O3, with 70 to 75 pct recovery of spodumene. Two flotation separations are required: the simultaneous removal of mica, feldspar, and quartz as a froth product using a cationic collector, and the subsequent removal of iron-bearing minerals as a froth product while spodumene is depressed as a tailing. SINCE the close of World War II there have been numerous developments resulting in the increased use of lithium by industry. Notable among these has been the development of an industrial lubricant, based on lithium stearate, which is fluid at low temperatures, stable at high temperature, and insoluble in water. A new bleaching agent, lithium hypo-chlorite, has also been developed recently.' Other well-known uses are listed below: 1—Lithium oxide in ceramics reduces firing time, lowers melting temperatures, lowers thermal expansion, raises refractive index, and improves chemical resistivity. 2—Lithium carbonate and lithium strontium nitrate are used in pyrotechnics for their brilliant red color.' 3—Lithium chlorides and fluorides are used as fluxes for welding aluminum and magnesium.' 4—The affinity of lithium for nitrogen is the basis for a process used in purifying helium." 5— Lithium chlorides and bromides are used in air conditioning for their powers to absorb organic amines, ammonia, and smoke.6-—Lithium hydride has been used as a source of hydrogen to inflate life rafts and balloons used by the Air Forces and Navy.' 7— Lithium metal and lithium hydride are useful in the atomic energy program in connection with the production of the isotopes of hydrogen." During the 1942-45 period of World War 11, Solvay Process Co. operated a flotation plant with a daily capacity of 300 tons of ore for the production of spodumene concentrate near Kings Mountain, North Carolina. The operation was shut down upon reduction of wartime demand for lithium chemicals, and until recently there has been no production from the Carolinas. In April 1950 an investigation of the problem of spodumene flotation from North Carolina ores was begun at North Carolina State College Minerals Research Laboratory at Asheville, N. C. This laboratory, operating under the combined auspices of North Carolina State College, North Carolina Department of Conservation and Development, and the Tennessee Valley Authority, undertook the spodumene project at the request of Foote Mineral Co. of Philadelphia. The work, involving a period of 15 months of intensive batch and pilot plant investigation, was completed in June 1951 and resulted in development of a process for concentration of spodumene by flotation which has been hereto unrecorded in the literature. A similar approach has been used before on iron, ilmenite, and other minerals, but the literature shows no record of its having been applied to spodumene. Parts of the process are now being used on a commercial scale at the Foote Mineral Co. plant near Kings Mountain, N. C., which has been in production since July 1951. It is the purpose of this paper to describe some of the results of the investigation. The Orebodies Spodumene-bearing pegmatites occur in a narrow belt 24.5 miles long and 1.8 miles wide extending southwestward from Lincolnton to Grover, N. C. According to statements judged to be conservative, the tin-spodumene belt of the Carolinas contains an estimated 4,300,000 tons of pegmatite ore averaging 15 pct spodumene. This amounts to "a reserve of at least 650,000 tons of spodumene (more than 20,000 tons of metallic lithium) to a depth of 100 ft."' This figure includes only bodies having an average thickness of 35 ft and length of 550 ft. There are hundreds of pegmatites in the belt, many of which are less than 10 ft wide. The largest pegmatite in the area has a maximum thickness of 395 ft and maximum length of 3250 ft.' These larger pegmatites are composed principally

Jan 1, 1954

By Orville R. Lyons

THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,1 but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913,8 by the United States Bureau of Mines in 1938,4 by Hancock in 1947,3 and by the national French research agency Cerchar in recent years.2 In 1950 Anderson' proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or ±0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1952