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By Charles L. Mantell, George Ferment

This investigation determined the jeasibility of current-potential curves as an analytical tool for monitoving manganese electroicinning solutions for metallic impurities. Nine metallic impurities were studied: trickel, cobalt, silver, copper, zinc, molybdenum, catlmiun magnesium, and sodium. The individual effect of each metallic irzplrl,iLy on the standard point-izatiorr was determined for a range of 'concentration. Not all of Ihe impurities affected the polarization curve; correlation between transition current and cotrcetztration of impurity. Molybdenum had an uncorrelated effect on the polarization curie. The effects of binary mixtures of impurities were studied to see if the transition current of the mixture could be predicted. Interactions occurred between impurities which prei'etzted the pvecliction the transition current of tile rrlisLitr.e by additive laws. The polarization curve was shown to be sensitive to metallic impurities which affect the current efficiency of a manganese cell. THE application of current-potential curves in manganese electrowinning is not new but played an important part in the conversion of an inoperative large-scale pilot plant into a continuous comnercial operation.1"" The effects of trace metallic impurities in manganese electrowinning solutions on cathode current-potential curves,5-19 specifically nine impurities (nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium) were studied for a range of concentrations. Cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity: molybdenum had an uncorrelated effect. Binary mixtures of impurities were studied to de-termine if the transition current could be predicted from the values for the individual constituents. Interactions between impurities prevented the prediction of the transition current of the mixtures by an additive law. The polarization curve was shown to be sensitive to metallic impurities which affected the rurrent efficiency of a manganese cell. The electrowinning of manganese relies upon maintaining a high-purity electrolyte. Purification schemes were developed to remove all of the heavy metals, the magnesium and calcium. Concentration limits have been established for single impurities. With high-purity electrolytes, favorable cell efficiencies are consistently obtained; but with impure solutions there is a reduction in efficiency. With the rapid rise to commercial prominence of electrochemical processes, there has been a lag in developing rapid methods for determining whether an electrolyte is sufficiently pure for efficient electrolysis. The most sensitive test for impurities is the behavior of the electrochemical cell. Impure electrolytes will cause a serious reduction in cell efficiency, and in many cases metal deposition will be prevented or reversed. The effects of impurities are not usually evident until after long periods of electrolysis, resulting in a disruption of the process. A method which could predict the behavior of an electrolyte in terms of cell efficiency prior to reaching the commercial cell is needed. Van Arsdale and Maier," Allmand and Campbell,a1'22 and others attempted to develop an electrochemical process for manganese,"3"29 but all met with some degree of difficulty. Jacobs et a studied the effects of metallic impurities in manganese electrowinning. Plant methods were based on a 2-hr plating in a small electrolytic cell. The final method was based on a 24-hr plating run, performed in a relatively large test cell. Here, current efficiencies were calculated with and without impurities in the electrolyte, and the critical concentration was established as the maximum amount of impurity that the electrolyte could tolerate before there was a serious loss in efficiency. The amount of impurity that could be tolerated decreased as the plating time increased, indicating deposition of the impurity. This test duplicated the conditions of commercial practire, and was sensitive to impurities. Small amounts of impurities significantly affect the hydrogen overvoltage at a metal surface, increasing or decreasing it depending upon the nature of the impurity. ockris established the limit for the onset of poisoning at 10-l moles per liter. The effects of impurities were studied by potential-time curves at a constant current density. The technique did not lend itself to rapid analysis in that several hours were needed to establish stable potential-time curves. Serfass and coworkers3' developed calorimetric and spectrophotometric techniques for analyzing for trace impurities. Our method4'" is based on current-cathode potential curves produced by continuously changing the cell voltage at a programmed rate. Starting with a clean stainless-steel cathode, the cell voltage was initially adjusted to yield zero current: the program was then started and the current was plotted as a function of the cathode potential. Fig. 1 is a typical current-potential curve. In initial region A the hydrogen-evolution reaction predominates and the polarization curve

Jan 1, 1967

By D. T. Peterson, F. A. Schmidt, J. D. Verhoeven

The velocity of mig-ration of these solutes in thorium metal due to a high amperage dc current was measured at several temperatures. All three solutes migrated in the same direction as the electron flow. Diffusion coefficients were combined with the migration velocities to predict the steady-state concentration profile. Electrotransport was shown to be an effective method of removing carbon, oxygen, and nitrogen from thorium and resistance ratios several times larger than for crystal bar thorium were achieved. However, the maxirnum attained purification was well below the predicted values, apparently due to some form of contamination. THE migration of solutes in metals when a high current density dc current is passed has been known for many years. This phenomenon has been the subject of a number of reviews published in recent years.l~* Many of the earlier investigators of electromigration of interstitial solutes interpreted the direction and velocity of migration on the basis of a charge on the solute particle. This interpretation is unclear because, in a given experiment, one cannot separate the contributions to the force moving the solute which arise from the charge on the solute in an electric field gradient and the momentum transfer from the scattering of the electrons or holes. There have been only a few quantitative measurements of interstitial migration velocities and some of these have been characterized by poor accuracy or by errors in the analysis of the experiment. The electrotransport mobilities of carbon, nitrogen, and oxygen in thorium were determined by observing the rate of movement of a discontinuity in the concentration profile. This method was used by Carlson el a~.~ to determine the mobilities of interstitial solutes in yttrium and its advantages are discussed in that paper. The specimen is essentially a pair of semi-infinite, bar-type diffusion couples. The electro-transport velocity was measured by observing the displacement of the mean concentration point in a measured length of time. The diffusion coefficients were calculated by the Grube method from the concentration profile. The transport mobilities and diffusion coefficients can be used to predict the concentration profile in an electrotransport experiment of a given time, current density, and specimen length. At long times a steady state will be reached such that the natural logarithm of the concentration of each solute varies linearly along the bar with a slope which is equal to the velocity of the migrating solute divided by its diffusion coefficient. The estimation of the purification potential of electrotransport is discussed by ~erhoeven.' A comparison of the concentration profile and the purification which should be expected from known solute velocities and diffusion coefficients with that which is obtained in an experiment can be very useful in indicating whether the maximum possible purification has been achieved. EXPERIMENTAL METHOD The apparatus used in this study consisted of a sample chamber which was equipped with two electrodes, a sight glass, and a flange for mounting to a high-vacuum system capable of obtaining pressure of 2 x lo-? Torr. The chamber was made of stainless steel and was 4 in. in diam and 6 in. long. The seal between the electrodes and the chamber was made with "0" rings and compression bushings. The thorium specimens were threaded and screwed into tantalum "U"-shaped adapters attached to the ends of the electrodes. This arrangement is shown in Fig. 1

Jan 1, 1967

By J. W. Town

The Bureau of Mines made continuous-circuit beneficiation studies to determine the optimum conditions for concentrating phosphate minerals from the intermediate-and marginal-grade ores of the Phosphoria Formation in southeast Idaho. Intermediate-grade ore was represented by a sample from Georgetown Canyon and marginal-grade ore from the Gay mine near Fort Hall. Two flow-sheets were developed: The first involved roasting, attrition scrubbing, sizing to remove a concentrate, grinding of the oversize, des liming, and flotation; in the other flowsheet roasting was eliminated. Controlled attrition scrubbing was used to remove clay and silt-size quartz particles imbedded in the phosphate pellets without breaking the pellets. The minus 35-plus 200-mesh fraction was removed by sizing as a finished acid-grade concentrate. The plus 35-mesh material was ground in a rodmill to minus 35 mesh and recycled to the attrition scrubber. The minus 200-mesh fraction was des limed at about 800 mesh to remove clay slimes and floated with 3 to 4 pounds of emulsion per ton of feed. The aqueous fatty-acid oil emulsion consisted by weight of 3 parts No.2 diesel oil, 3 parts crude tall oil, and 0.5 part water-soluble petroleum sulfonate.

Jan 1, 1967

By M. R. Tek, F. F. Craig, J. O. Wilkes, C. S. Goddin

The waterflood performance of a water-wet, stratified system with crossflow is computed by a finite difference procedure. The effects of five dimensionless parameters on tile oil displacement efficiency, water saturation con-tour.7 and crossflow rates are evaluated in the absence of gravity forces. Crossflow due to viscous and capillary forces is shown to exert a significant effect on oil recovery in a field-scale model of a two-layered. water-wet sandstone reservoir. The crossflow is at a maximum in the vicinity of the front advancing in the more permeable layer. Under favorable mobility ratio conditions, the comparted oil recovery with crossflow always is interrnerliate between that predicted for a uniform reservoir and that for a layered reservoir with no crossflow. INTRODUCTION The important erects of reservoir heterogeneity on waterflood performance are commanding increased attention in the technical literature. Much of this attention is centered on two categories of layered reservoirs: those in which layers are non-communicating and those in which crossflow of fluids occurs between the layers. In the first category, the reservoir is assumed to consist of discrete layers, each uniform within itself and differing from the others only in such properties as thickness, porosity and absolute permeability. The performance within each layer is calculated by one-dimensional flow theory, and the performance of the total reservoir is obtained by summing individual layer performances. Capillary and gravity effects usually are not considered. Representative publications dealing with thi5 type of reservoir are those of Stiles,' Dykstra and Parsons,' Hiatt,3 Warren and Cosgrove' and Higgins and Leighton." Prediction of performance for reservoirs in the second category is considerably more difficult since viscous, capillary and gravitational forces all play important roles in causing crossflow between layers. A number of authors have investigated the simpler problem of two-dimensional displacement flow in a stratified system with a mobility ratio of unity and negligible capillary and gravity effects.'; Others have considered two-dimensional, non-steady-state flow of a single, slightly compressible fluid in a stratified reservoir. A limited number of laboratory oil displacement tests in layered models with crossflow have been reported. Miscible floods (with resultant zero capillary forces) in layered five-spot models were conducted by Dyes and Braun," who studied the effect of mobility ratio with zero gravity forces, and by Craig et al. 12 who studied the effect of gravity forces at constant mobility ratio. Waterfloods in layered five-spot models (with cross-tlow due to capillary, viscous and gravity forces) were conducted by Gaucher and Lindley,"' who showed the effect of gravity forces in causing underrunning of the injected water and by Carpenter, Bail and Bobek, 14 who demonstrated the reliability of Rapoport's" dimension-less parameters for scaling layered systems. Waterfloods in rectangular layered models were conducted by Richardson and Perkins."' who investigated the effect of velocity at constant mobility ratio and with zero gravity forces, and by Hutchinson," who studied the effects of varying mobility, layer permeability and layer thickness ratios. The differential equations which rigorously describe waterflooding in a heterogenous porous medium are non-linear and do not facilitate analytical solution. By using finite difference approximations it is possible to obtain a solution to any desired degree of accuracy. Such a solution, using an alternating direction implicit procedure (ADJP), is described by Douglas, Peaceman and Rachford.18 In the present study, a computer program using ADJP explores systematically the effects of important parameters on waterflood performance of a two-dimensional, two-layered, field-scale model of a water-wet sandstone system. Particular attention is given to evaluation of the water saturation contours and crossflow rates at the interface between layers to gain improved understanding of the crossflow mechanism. PROCEDURE BASIC: FLOW EQUATIONS The basic flow equations for two-dimensional, two-phase, immiscible, incon~pressible flow in a porous medium are:

Jan 1, 1967

By R. E. Lindstrom

The mineral bastnasite is utilized to describe alternate processes for the extraction and separation of the rare-earth elements by solvent extraction. The rare earths can be acid-leached directly or fused with NaOH before acid leaching. Cerium, the major constituent, can be recovered by fractional precipitation, fractional leaching, or solvent extraction with tri-nbutyl phosphate. The latter process is capable of producing 99.5-percent pure CeO2 at 98+ percent recovery. Lanthanum is subsequently recovered by fractional precipitation or solvent extraction with a nitrogen-based extractant. A 20-stage mixer-settler operation with a primary amine extractant results in a 95-percent pure La203 fraction at 96 percent recovery. Europium is amenable to extraction from most of the remaining rare earths with an organophosphate extractant. Selective stripping of the europium, followed by reductive precipitation, produces high-purity Eu203. Another possibility for europium purification involves the differential extraction of europium with an amine followed by a sub- sequent reducing strip. Separation of the remaining elements is more difficult but can be accomplished with amine or quaternary ammonium extracts. Typical separation factors achieved are 3. 8 for praseodymium-neodymium and 10. 5 for neodymium-samarium.

Jan 1, 1967

By James A. West

The South Asian countries of India, Pakistan, Afghanistan, Ceylon, Nepal, Bhutan, and Sikkim arc to varying-degrees just beginning to achieve significant economic and industrial development. These countries are richly endowed with certain mineral resources, and development of these resources is being accelerated. In 1965, the mineral industry remained a relatively small sector of the region's economy, accounting for only about 1 percent of its estimated gross national product of $62,528 million. Nevertheless, the estimated $630 million total value of minerals produced in South Asia during 1965 represented an increase of nearly 15 percent t over that of 1964. India continued as the dominant mineral producer of the region, accounting for 85 percent of the total value of all minerals produced ill 1965. India increased its output of iron ore, manganese, mica, coal, and petroleum. Pakistan accounted for 13 percent of the value of the region's output and recorded increased output of iron ore, chromite, coal, natural gas, and most other minerals. The small mineral industry of Ceylon attained remarkable growth in the production of ilmenite, graphite, and gem stones. The mineral industry of Afghanistan remained relatively insignificant, although development of large known resources of natural gas was continued, Nepal, Bhutan, and Sikkim produced no commercially significant quantities of minerals in 1965.

Jan 1, 1967

By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.' The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By Leo A. Schrider

A prediction for oil recovery from a pilot waterflood in the Kane oil- field, located in Elk, Forest, and McKean Counties, Pa., was made and compared to actual field performance. Water-injection and production histories, well logs, other field data, and results from laboratory tests of core material were used in this analysis. Performance of the pilot waterflood, initiated in January 1963, was predicted using a modified Craig, Geffen, and Morse calculation technique. Maximum recovery from this low permeable, preferentially oil-wet formation was predicted to be about 22,500 barrels of oil after 300,000 barrels of water had been injected into the pilot waterflood area. After additional field data were collected it became necessary to reevaluate the pilot waterflood area. The gas saturation prior to the waterflood was estimated to have been 20 percent, based on an assumption regarding the required volume of water injected to initiate oil production. In view of the actual field performance, a gas saturation of 13 percent is indicated. When this gas saturation and the method originally proposed by Craig and others are used) the predicted results are more representative. In December 1965, field performance was further analyzed using a hyperbolic-decline curve as presented by Arps. Based upon this evaluation method, the pilot water flood in the Kane sand should produce 37,000 to 42,000 barrels of oil with the injection of 300,000 barrels of water into the pattern. By continuing this secondary-recovery project to a reasonable economic limit, ultimate oil recovery may be as much as 50,000 to 55,000 barrels, or 129 to 142 barrels per acre-foot from 36.5 acres.

Jan 1, 1967

Jan 1, 1967

By Mark J. Klein

The precipitation of nitrogen in quenched and aged CY-35 at. pct Re was followed by internal-friction and electrical-resistivity measurements. It is shown that the precipitation kinetics of nitrogen from solution are many orders of magnitude lower in this alloy than in chromium. The reluctance of nitrogen to precipitate from sol~ction can be attributed to the composilional r-eadjustnzents required in the z.icinity of a chromium nitrade particle for gowth to occur. AS part of an investigation of the mechanism by which rhenium increases the low-temperature ductility of chromium and other Group VI-A metals, it was of interest to compare the concentration of interstitial elements retained in solution in chromium with that of a ductile Cr-Re alloy. The presence of certain interstitial elements in chromium has been shown to decrease its ductility1-5 and, of these interstitials, nitrogen is believed to have the most detrimental effect on mechanical properties. Thus, a comparison of the disposition of nitrogen in chromium with that in a ductile Cr-Re alloy might provide information about the mechanism whereby rhenium enhances the ductility of chromium. In previous internal-friction studies it was shown that the equilibrium solubilities of nitrogen in chromium and Cr-35 at. pct Re did not differ greatly.= However, results indicated that the actual concentration of nitrogen retained in solution at ambient temperatures is likely to be considerably greater in the alloy than in chromium because the precipitation kinetics of nitrogen are greatly retarded by the addition of rhenium. The objective of this investigation was to study the kinetics of nitrogen precipitation in Cr-35 at. pct Re in greater detail and to obtain information concerning the mechanism of nitrogen precipitation in this alloy. The properties studied were internal friction and

Jan 1, 1967

By B. H. Bergstrom

The Gaudin-Meloy1 size distribution equation requires the evaluation of two constants, xo and r. The common log-log representation of a screen analysis as cumulative weight percentage passing versus size, readily yields the required constants as illustrated for curves A and B in Fig. 1. The 100% passing (y = 1.0) size is simply x,. If the straight portion of the curve be extrapolated to the 100% passing (y=1.0) abscissa, the intercept is the Schuhmann size modulus, k. The ratio of xo to the size modulus, k, is r as shown: The Gaudin-Meloy equation requires that the slope, a, of the size distribution approach unity in the finer sizes, as is the case for curves A and B. Often distributions are better characterized by slopes other than unity. The schuhmann2 equation is able to represent these distributions if the upper portions of the curves are ignored. Empirically, the Gaudin-Meloy equation can be modified to yield slopes other than unity by writing it as Here, a is the familiar Schuhmann slope, and xo is the 100% passing size. The value of r is still given by Eq. 2. Eq. 4 with its easily determined constants is more versatile than either the Schuhmann or the Gaudin-Meloy equations, since a wide variety of size distributions can be closely described. It is easier to fit than the Rosin-Rammler3 equation, and has the advantage that the top size, x,, is finite. REFERENCES A. M. Gaudin and T. P. Meloy: Model and a Comminution Distribution Equation for Single Fracture, AIME Transactions, 1962, Vol. 223, pp. 40 to 43. R. Schumann, Jr.: principles of comminution, I., size Distribution and Surface Calculations, AIME Technical Publication No. 1187, 1940. P. Rosin and E. Rammler: The Laws coverning the Fineness of Powdered Coal, J. Inst. Fuel, 1933. Vol. 7, p. 29.

Jan 1, 1967

By L. F. Heising

The Bureau of Mines evaluated 42 composite samples from selected Michigan-Wisconsin iron formations by reductive roasting-magnetic separation and flotation at minus 325 mesh. Samples having poor to marginal response on initial examination by conventional methods were reevaluated by finer grinding, by reagent suite modifications, and by selective flocculation-desliming techniques. Results ranged from excellent on Menominee Range samples to relatively on Gogebic Range ores. Marquette Range samples ranged from responsive to nonresponsive, depending upon grain size and mineral association.

Jan 1, 1967

By D. W. G. White

The surface tension of zinc has been determined by the sessile-drop method in a progvam emphaszzing detailed experimental care. The surface tension oj. the pure metal was measured over a range of ternperature from the melting point (419.6"C) to 540°C. At the melting point, the suvface tension of zinc was found to be: 1) 99.99+ pct Zn - 757.0 5 dynes per cm 2) 99.999+ pct Zn - 761.0 5 dynes per CI 3) 99.9999 pct Zn - 76'7.5 5 dynes pev cna From experiments carried out in a closed, isothermal cell, the temperatuve coejyicient of the surface tension (6y/6T)p, , of zinc xas found not to be negative but to be postiue. A positive tenzperatre coefficient indicates a greater depee of order in the surface than in the body of the lquid. Houlezer, by delibevately inducing continuous zaporization, a temperature coefficient of su)face tension with a negative slope can be produced. The work reported herein was undertaken as part of a larger program of fundamental research on the properties of molten zinc and zinc alloys. This program grew out of a continuing interest at the Mines Branch in the behavior of liquid metals in the foundry and of a desire on the part of the zinc industry for reliable basic data. The work was originally begun in cooperation with the Consolidated Mining and Smelting Co. Ltd., Trail, B.C., and was subsequently continued from 1960 to date in association with the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. Although the surface tension of liquid zinc has of course, been measured before, as Table I and Fig. 1 demonstrate, there is not good agreement among the existing values. Such disparities arise because sources of experimental error are insufficiently controlled. This situation places the reader in doubt. One result may be correct within narrow limits—even fortuitously—yet, because there is not agreement between several values, none can be accepted with conviction and all become suspect. It seemed, therefore, in the circumstances, that there was room for further work embodying considerable emphasis on experimental care in order that, within a small margin of error, an accurate value might be obtained. It was in this spirit that the work was undertaken. METHOD The sessile-drop method -as adopted for this work. In this method, when applied to liquid metals at elevated temperatures, the outline of the meridional section through a drop resting freely on a horizontal surface is recorded photographically. Certain parameters

Jan 1, 1967

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

By E. A. Twichell

An entirely new concept in the effective utilization of magnetic, energy has resulted in a major break-through in the design of magnetic separation equipment. One of the first applications of this concept has resulted in the development of a Permanent Magnetic Wet Drum Separator with strength .and operating characteristics equal to Electro Wet Drum Separators. Prior to this development when strength and adjustability were required, electro wet drums were specified even with all their drawbacks. The electros, by nature, are subject to coil failure or burnout, over-heating and loss of strength, high power consumption and generally high maintenance. Now the high strength and the adjustability, formerly the exclusive property of electros, has been engineered into permanent wet drum separators. These units combine maximum field strength in the separation zone with strength adjustment to suit changing conditions. Adjustment can be effected while the drum is in operation without stopping either the feed or the drum.

Jan 1, 1967

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting' thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By Edward I. Renouard

"THE mineral industry is constantly undergoing changes and facing challenges, and today we are in the midst of another serious one -namely, manpower requirement at every level in the mines, shops and plants. In the not too distant past we had a situation where labour was plentiful, although the equipment, by present-day standards, was quite inadequate, and that's easily understandable when you look back at the primitive methods by which our Western mines were first developed and operated, and then improved by the inventiveness and ingenuity of man.I'd like to show you a few slides from drawings made by Buck O'-Donnell which illustrate some of yesterday's methods of mining. Some of you probably had first-hand experience with some of these so you know they were tedious, time-consuming and involved a lot of heavy labour.Taking the Anaconda Company operations at Butte as an example, we can see what has happened in just the past ten years. In August of 1956, the Butte mines had 5,516 day's-pay employees and 976 salaried employees, for a total payroll of 6,492. In August of this year, there were 3,645 day's-pay employees and 605 on the salaried roll, for a total of 4,250. The number of contract miners had gone from 1,347 in 1956 to 606 in 1966 and that of other underground miners from 2,893 ten years ago to 1,149 this year. Along with these changes, however, another change of special significance has taken place, and that is in the number of skilled craftsmen, surface engineers and so on required for our operations. In 1966, we had 1,890 of these people, 600 more than in 1956 and nearly three times as many as just twenty years ago."

Jan 1, 1967

By H. R. McCabe

"The study of a detailed series of structure and isopach maps of the Palaeozoic strata of southwestern Manitoba indicates that the principal Palaeozoic tectonic elements -the Williston Basin and Elk Point Basin -have been modified to a considerable extent by major tectonic features of the Precambrian basement. The principal basement feature is the break between the Churchill and Superior provinces, which coincides roughly with the Manitoba-Saskatchewan border. East-west-trending orogenic belts within the Superior crustal block may also be reflected to some extent in later Palaeozoic movements. In addition, the Superior crustal block, as a whole, appears to have had a slightly different response to the tectonic forces, giving rise to both basin subsidence and basin uplift. During periods of deposition, especially during Ordovician time, the Manitoba portion of the basin appears to have undergone a relatively higher rate of subsidence, whereas during periods of erosion relatively greater amounts of uplift and truncation have occurred. As a result, the depositional and erosional patterns for most of the Palaeozoic formations in southwestern Manitoba are somewhat anomalous relative to the regional basin framework.Some prominent Palaeozoic structures probably are the result of salt solution and differential compaction caused directly or indirectly by relatively minor tectonic movements related to Precambrian basement features. In particular, the prominent hinge line at the edge of the Devonian Prairie Evaporite salt basin may be due, in large part, to salt solution. Numerous other small structural lows, structural highs and isopach thicks, probably resulting from salt solution, occur along the salt edge and have been important in modifying and controlling Mississippian oil accumulation in the Daly-Virden producing area."

Jan 1, 1967

By O. J. Kensok

THE literature contains three previous studies of the chemical activities of Cd-Mg alloys: Trumbore, Wallace, and craigl obtained chemical activities of magnesium at 543" by performing electromotive-force measurements; Borg and irchenall calculated activities at 590°K based on vapor-pressure measurements of cadmium over Mg-Cd alloys by the Knud-sen effusion method; and Terpilouski and arcka measured the chemical activities of magnesium in the liquid state by means of electromotive-force measurements. In this study the vapor pressure of cadmium was determined over nine solid Cd-Mg alloys in the temperature range 571" to 697°K by the Knudsen effusion method. This study was prompted by the lack of precision in the data reported by Borg and Birchenall. Knudsen cells used during this study were fabricated from 0.020-in.-thick tantalum tubing. The tops and bottoms of the cells were cut from 0.010-in.-thick tantalum sheet, press-fitted, and welded in place. The orifice was drilled in the cell top and subsequently reamed to a knife-edge thickness. The diameter of the orifice was measured with a traveling microscope capable of reading 0.0001 cm. The sample was heated by means of a resistance

Jan 1, 1967

By J. B. Boniwell

The INPUT electromagnetic prospecting system was originally developed by Dr. A. R. Barringer in an effort to increase the sensitivity and penetration of airborne EM methods. Although brought to an operational state some several years ago, it is only through relatively re-cent modifications and testing that some of the potential of the system has been fully realised. This is brought into perspective by some recent results over known ore deposits and geologic environments.

Jan 1, 1967