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By J. D. Audley Smith

Heine's " blue test" for copper, as described by the authorities generally, calls for a set of standard colors; and there has been some discussion concerning the relative superiority, for this purpose, of sulphate and nitrate solutions. The whole matter evidently hinges on the preservation of the standard colors in well-stoppered bottles. The apparatus described by Q. L. Heath* cannot be much improved, when very accurate readings are required. The following method was devised for the purpose of doing away with preserved sets of standard colors, by making a fresh standard for each batch of assays. The solutions are prepared in the usual way, each ammoniacal solution being filtered into its separate bottle, and then filled up to the containing-mark and thoroughly mixed. A similar color-bottle, with an " S " etched upon it, to distinguish it from the other bottles, which are numbered to correspond with the samples, is kept to run the standard. About 150 C.C. of water is put into it, and then the amount of acid (sulphuric or nitric) present in each determination, followed by 30 C.C. of ammonia (s. g. 0.90), which should make the mixture strongly ammoniacal. The liquid is now made up almost to the containing-mark (200 c.c.), say within 1 C.C. The lowest assay is selected first and placed alongside the standard, which, at the beginning, contains no copper. A copper-solution is then dropped into the standard from a burette ; and after each addition the bottle is well shaken and compared with the assay-sample. This operation is repeated until the two shades match exactly, when the burette is read and the assay-result is calculated. The assay next in order of depth of color is now taken and treated in the same way, and so on, until the batch is completed. It

Jan 1, 1901

By Samuel Doak

THE utilization of rotary kilns, of the well-known cement type, for the preparation of iron ores, for the blast furnace, has become of considerable economic importance within the past 10 years in certain localities, notably those where the native ores are lean. Such kilns may be used simply for the agglomeration of ores too fine to be charged into the blast furnace (i.e., ores whose loss in the dust catchers is excessive, and whose fineness is detrimental to the working of the furnace), or for the desulphurization of lump and fine ores the sulphur content of which does not exceed 6 or 7 per cent. The desulphurizing action can be combined with that of agglomeration provided the kiln is sufficiently large. Other processes have been developed for the same purpose, but while I am not able to draw a comparison between them by reason of lack of sufficient data, it is safe to say that the kiln, if properly dimensioned for the character of ore to be treated, will compare favorably in its results, both as to economy and quality of product, with any other process. It is not, however, as well adapted for the treatment of flue dust, as is a sintering operation, on account of the large percentage of fine coke contained therein. Any combustible entering the kiln at its feed end renders the process very much more expensive and unsatisfactory on account of the difficulty of controlling the temperature, also because of the rapidity with which long "rings" form, due to the increased heat at the cooler end of the kiln. The greatest value of the kiln at present is in the treatment of pyrites cinder; that is, the residue from pyrites ore after the extraction of the greater part of the sulphur. This cinder, while high in iron content, has too much sulphur remaining in it to be allowed to form a large part of the blast-furnace burden, without further treatment. It will range in metallic iron from 42 per cent., representing a very low-grade cinder, from a domestic pyrites, to 64 per cent. of the residue from the best Spanish ore, and the corresponding silica content will vary from the maximum of about 25 per cent. to 1 ½ per cent. The residual sulphur depends largely on the type of burner used in the original desulphurization. In general, the leanest original ores retain the greatest amounts of sulphur. In

Jan 9, 1915

By N. A. Gjostein

The self-diffusion coefficient D, for a surface near the (100) plane in copper was determined by means of the Mullins theory of thermal grooving, and was found to obey the Arrhenius relationship, and Do = 6.5 x 10' sq cm per sec. Suppression of surface diffusion by chemisorbed impurities encounters difliculties as a satisfactory explanation for the large Q, and Do. Instead, a model is presented which indicates that Q,, as determined by a mass-transport technique, may involve both the energy needed to form an adsorbed atom from a ledge in the surface as well as that for the movement of the adsorbed atom.; LITERATURE reviews1-3 indicate that the mechanism of self-diffusion on metal surfaces is not clearly understood. The lack of experimental data on the temperature variation of the surface self-diffusion coefficient DJ has contributed greatly to this situation. Radioactive tracer techniques4-rn have been used to measure Ds, but for many years only Nicker-son and Parker8 had determined (for polycrystalline silver) an activation energy B, and a frequency factor Do for the surface self-diffusion process. Even in this case, a mechanism could not be clearly inferred because it was suspeted7 that a contribution from volume diffusion was not taken into account by the investigators. Some later work by Li and parkere on polycrystalline gold, in which they obtained essentially the same results as for silver and in which volume diffusion could be accounted for, seems to invalidate this criticism. In 1957, Mullins10'11 developed the theory for the thermal grooving process. This advance has opened a new and promising technique for measuring the surface self-diffusion coefficient Ds. Recognizing that a thermal groove may form by several different mass transport processes, Mullins first consideredlo the cases where a) the groove forms by evaporation and condensation or b) by diffusion along the groove surface, in either case, in a system where a metal surface is in contact with only its dilute vapor phase. In a later paper," he extended the treatment to cases where the groove forms by volume diffusion into c) the solid phase or d) by mass transport through a passive gaseous phase at 1 atm pressure. The time dependence of the groove dimensions and the shape of the groove profiles predicted by Mullins' treat-

Jan 1, 1962

By D. A. Schemnitz, O. W. Ellis

Certain alloys1 that, as a result of quenching, are retained in the form of homoaeneous solid solution are known to increase in hardness and strength on standing at room temperature or on heating at slightly elevated temperatures. Other alloys2 that, on rapid cooling, are held in the form of homogeneous solid solution, as, for example, certain steels, behave in like manner on heating to somewhat higher temperatures. The observed increase in the hardness and strength of these alloys, referred to as " aging"' or as "secondary hardness," is widely accepted as being occasioned, either in whole or in part, by the precipitation in submicroscopic form of such constituents as were held in supersaturated solid solution as a result of cooling in excess of a certain critical rate. In earlier discussions of the cause of age hardening or secondary hardness, the question of the hardness of the precipitated particles does not appear to have been raised. At present, however, the general opinion appears to be that age hardening and secondary hardness are occasioned by the precipitation of hard particles within the supersaturated solid substance.3 The authors may be wrong in their belief that the last is a prevailing opinion. Nevertheless, it is thought that the following experiments,

Jan 1, 1925

By O. W. Ellis

CERTAIN alloys1 that, as a result of quenching, are retained in the form of homogeneous solid solution are known to increase in hardness and strength on standing at room temperature or on heating at slightly elevated temperatures. Other alloys" that, on rapid cooling, are held in the form of homogeneous solid solution (as, for example, certain steels) behave in like manner on heating to somewhat higher temperatures. The observed increase in the hardness and strength of these alloys, referred to as "aging" or as "secondary hardness," is widely accepted as being occasioned, either in whole or in part, by the precipitation in submicroscopic form of such constituents as were held in supersaturated solid solution as a result of cooling in excess of a certain critical rate. In earlier discussions of the cause of age hardening or secondary hardness, the question of the hardness of the precipitated particles does not appear to have been raised. At present, however, the general opinion appears to be that age hardening and secondary hardness are occasioned by the precipitation of hard particles within the supersaturated solid substance.3 The authors may be wrong in their belief that the last is a prevailing opinion. Nevertheless, it is thought that the following experiments,

Jan 7, 1924

By Carl S. Westerberg

Coal preparation practice and trends follow, among other factors, production trends in any given area. Considering an area the size of a state, some broad predictions may be made after a review of the annual production records. As this paper is concerned with coal cleaning in Utah, data on its production record are pertinent. Table 1 shows the percentage relation of coal production in Utah to the national total as a single figure up to 1935 which includes all recorded production. From 1935 through 1947 these data are presented by years. It is evident from these data that the production of Utah coal is ascending. The reason for this trend is industrial growth in the West resulting in a population shift which accounts for more people than the normal increase would supply together with Utah's relatively fortunate geographical location and its abundance of good-quality coal. Utah is also hopeful of supplying more coal in the future for West Coast power generati0n.l

Jan 1, 1949

By R. H. Moore

The data for diffusion in dilute binary alloys with the Solvents Ag, Cu, Ni, Fe. Al. and Pb hare been correlated as a function of atomic volume. Linear equations of the form: Q = b - a log V are obtained with constants "a" and "b" ciuirac-teristic of each solvent metal. In most cases. 3-d In recent years measurements of diffusion coefficients in solid binary alloys. using small concentrations of radioactive isotopes. have resulted in accumulation of highly reproducible data. Such and 4-d transition elements correlate on separate straight lines from those which serve to correlate the non/ransition elements. The data for the uon-transilion elements diffusing in silver and copper liave been fitted by least-squares analysis. It is concluded that the size and charge effects which determine the magnitude of the activation energy for diffusion are a function of atomic volume. systems represent the simplest possible examples of chemical diffusion since solute interaction effects can be neglected and Kirkendall-like phenomena do not occur. Generally it is found that thc diffusion rate of the solute is within an order of magnitude of the diffusion rate of the solvent. The differences have been attributed to the effect of size and to electrostatic interactions between the solute and solvent atoms.

Jan 1, 1965

By G. S. Baker, S. H. Carpenter

Langenecker has reported significant reduction in strength of high-strength metals during ultrasonic t'ibration. Decreases in static yield stress an order of magnitude greater than the calculated stress amplitude of vibrations were reported by him for a stainless steel and for tungsten. in the present work, attempts were nzadc to verify such large reductions in yield and flats stresses using resonant librations of measured amplitudes. The results show that both the soft metals (copper and aluminum) and the high-strength metals (sleels) hare reductions in yield and .flow stresses no larger than the stress amplitude of libration. BLAHA and Langenecker,' investigating the effect of vibratory stresses on the deformation of zinc and aluminum, found a decrease in the static yield and flow stresses approximately equal to the vibratory stress imposed. Langenecker later extending this work to high-strength metals such as stainless steels and tungsten2 found a much larger effect. In these metals the static yield and flow stresses decreased by an amount more than an order of magnitude greater than the calculated vibratory stresses. It was suggested that this phenomenon could be a serious hazard to high-strength structures in an acoustic environment, such as a large rocket at launch, or could be used advantageously in the working of hard-to-work materials such as the refractory metals. Langenecker and others3 have investigated the effect of high-amplitude vibrations on many metal-forming operations. The results have been quite favorable with usually a large decrease in the energy necessary for the forming operation. The processes, however, involve large frictional forces and it is not clear whether the decreases in forming forces are to be ascribed to decreased friction or to decreased flow stresses. The present paper reports an attempt to determine the effect of accurately known vibratory stresses on the static yield and flow stresses. I) EXPERIMENTAL TECHNIQUE The standard multicomponent resonator technique for measuring internal friction has been adapted to allow simultaneous high-amplitude vibration, internal-friction measurement, and tensile deformation. This has been described in detail elsewhere.4 Longitudinal oscillations of approximately 50 kc frequency are excited in a multicomponent resonator by a quartz transducer. A second transducer measures the amplitude of vibrations. Fig. 1 shows a schematic drawing of the resonator and grip arrangement and the displacement pattern produced. Since the centers of the dummy bars are at displacement nodes, they represent points where attachments will not materially affect the vibrations. The force is applied by a standard Instron tester. The sample may be deformed while simultaneously vibrating at up to 104 strain amplitude. 11) EXPERIMENTAL RESULTS The effect of high-amplitude vibrations on the yield and flow stresses of copper. aluminum, tantalum. a soft iron, and a stainless steel has been measured. In addition samples of tungsten vibrating at stress levels up to 10' dynes per sq cm have been subjected to static stresses near the static yield stress with no indication of macroscopic deformation. Fig. 2 gives typical results for 99.999 pct polycrys-talline copper. A vibratory stress of 7 x 107 dynes per sq cm is applied at points "a" and removed at points "h". The behavior of aluminum is identical. In agree-

Jan 1, 1967

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

Q: It is May 1961 at Bill Wrather's Washington house. Bill, think back to your first job after college. Wrather: Perhaps I ought to go back a little bit further than my first job. I entered the University of Chicago with the idea of studying law. My intention was to take a 4-yr liberal arts course and superimpose a law degree on that. But during my undergraduate work I fell under the influence of R. D. Salsbury. He decided I had some talent as a geologist and influenced me to take a geological course. Nevertheless, I did not give up the idea of law. While in school I took a spell of typhoid fever and almost died. The doctor recommended outdoor exercise, so a geological job seemed logical. W. H. Emmons was a graduate student in the University and he interceded with Dr. Hayes of the USGS. I went on the payroll as assistant packer at $60 a month. I had one of the most glorious summers I ever spent in my life. That fall and the following year I took law courses and became thoroughly convinced that I was cut out for a geologist rather than a lawyer. I finished up my law work in 1908 while waiting for a job with Bill Emmons, who was doing a careful study of Goldfield and Tonopah.

Jan 4, 1964

By R. O. Williams

A recent article by Chernock, Singer, Mueller, and Beck 1 which supports the use of the integral of I sin $ d$ for comparing fiber texture data does not settle what happens to I sin ø as ø approaches zero, where I is the diffraction intensity for poles oriented 0 deg from the fiber axis. They indicate that they believe that it should approach some constant value (that is, I increases without bound) and the fact that in reality it does not was a result of the diffraction

Jan 1, 1960

By P. C. Kapur

A principal first-order and a minor summation term contribute to the solution to the discretized batch-grinding equation when formulated in cumulative retained mode. Depending on the inter relations hips between the selection and breakage parameters, the minor term may be advantageously modified in a number of ways. The reduced grinding equations thus obtained are solved by iterations to give relatively simple solutions which are tested against experimental data. The irn-plications and advantages of the reduced grinding equations are briefly discussed. In many instances, the trajectory of the particle-size distribution in a batch mill may be extracted from a set of particle mass balance equations as follows

Jan 1, 1971

By V. J. Parks, Leonard Obert, A. J. Durelli

The state of stress in the region where core discing initiates has been investigated through the use of three-dimensional photoelastic models and the results of this study have been compared with those of a previous investigation of rock models. This comparison showed that discing initiates at a point of maximum shear stress, but that the magnitude of the shear stress, as determined photoelastically, is much larger than the shear strength of the rock as deter-mined from conventional triaxial testing. Moreover the shear stress required to produce discing is not constant, but depends on the applied stress field. Possible explanations for these effects are included in this article. In both exploration core drilling and overcore drilling to determine the stress in rock, occasional sections of the core obtained are broken into a series of discs.I* This discing phenomenon has been investigated in the laboratory to ascertain the state of stress required to produce it. The objective of the study was to obtain information that would make it possible to approximate the state of stress in subsurface rock from which disced cores are obtained. Referred to as the discing test, this laboratory study was conducted to determine the applied axial and radial loads required to produce discing in cylinders of rock from several sources. The dimensions of these cylinders are given in Fig. 1. Discing was produced by first applying an axial load to the cylinder and then diamond drilling the core along its axis. The radial load was then incrementally increased until discing initiated. The discs fractured or ruptured* on surfaces approximately normal to the axis of the core (planes A, B, C, D, E, Fig. 2). In many instances, the bottommost disc fractured before the drill had advanced past the points F and F', cre- ating a mush room-shaped fracture surface FEF'. Alternatively, it was also found that the same shaped fracture surface could be created by first drilling in an unloaded core to some point, say F and F', and then triaxially loading the core until fracture occurred on the plane FEF'. Jaeger and cook4 produced similar fracture surfaces in specimens subjected only to a radial biaxial load. From these laboratory studies and observations made in the field, it can be inferred that fracture or rupture initiates in the proximity of the lowest point in the kerf area, (at F and F', Fig. 2) and that the fracture or rupture surface progresses inward from this point. The experiments described above, however, do not provide any information as to the state of stress at the point at which fracture or rupture initiates. In the investigation discussed in the following sections, a three-dimensional photoelastic analysis was conducted to determine the stress distribution in the proximity of the kerf area of a triaxially loaded plastic (epoxy) cylinder containing a short section of core.

Jan 1, 1969

By David White

While a country is small and its coal fields are not many, it may be possible to classify its coals on some basis that avoids both overlap and inconsistency, and that may be satisfactory to the particular country, such as geographic distribution or geologic age, or regional uses. In the adjoining country, however, the coals may differ more or less; broad areas may have escaped the erasure of transition zones by erosion, and the stages of alteration of the coals may lead to a classification different from and even incompatible with that of the other country. Such classifications, developed primarily along national lines, are essentially opportunistic. Further, many even of the "use" terms that have been in more common employment with a degree of international application have lost their significance and value, due to changes in industrial methods and urban life. When the number of coal fields is large and the classification is designed to cover the coals of many countries, the groups or divisions into which the coals are integrated are found to verge one into another; and, though the main divisions may be so naturally composed and oriented that they are relatively distinct and readily separated as entities or units when taken by themselves, the sequence, through classes, groups, and subdivisions, is so complete that we find transition zones through which boundaries must be arbitrarily drawn with minute technical definition. This situation, which is conspicuously illustrated in the United States, is due to the progressive evolution of all coals, irrespective of geologic age, from peats to successively higher ranks, which, if the progressive alteration goes far enough, ends with graphite. This evolution is now firmly established and its complete acceptance is but a matter of time. A classification of all coals in all coal fields can not escape this fact and must take into account all the stages in the transformation of the fuel from rank to rank through division to division, and through group to group. The plan here outlined aims at a natural classification of coals based on their evolution from peats to graphite. As in other classifications, the differentiation of the various groups and divisions takes account of changes resulting from the progressive losses of moisture and .of oxygen of constitution; the relative conservation of carbon; the progressive increase in fixed carbon (inverse to the loss of volatile matter) in

Jan 1, 1930

TO THE BOARD OF DIRECTORS AND THE MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN: Herewith are submitted the report of the Treasurer for the year 1936 and the reports for the same year of the following committees: Admis¬sions, Membership, Papers and Publications, Library, Student Relations, and MINING AND METALLURGY. To these reports you are referred for details of the year's activities. Finances.-Income for the year was $173,091 including an appropria¬tion of $2500 from the Rocky Mountain Fund earmarked to defray expense for official visits to western Sections and student societies. This compares with $141,754 in 1935 and exceeds by more than $50,000 the income of 1933 wherein the low point during the depression was reached. The major items of increase were: $6,700 from current dues; $10,600 in initiation fees and dues of newly enrolled members; $10,800 from the monthly magazine MINING AND METALLURGY. Sundry small declines were offset by minor increases. Expenditures for the year totaled $176,007 compared with $148,361 in 1935. Major increases were $5,700 for MINING AND METALLURGY; $4,000 for TRANSACTIONS and TECHNICAL PUBLICATIONS; $1,500 for meetings; $1,300 for Local Section appropriations; $6,500 for Technical Division expense; $5,000 for Increase of Membership expense; and $2,500 for visits to Local Sections and educational institutions. Comment on several of these items will appear under subsequent heads. Net deficit for the year was $2,915, this sum being made up from the accumulated surplus. It is interesting to observe that the net excess of income over outgo for the five-year period 1932-1936, inclusive, is $760. Membership and Dues.-During the year there was a net gain in membership, including Members, Associates, Junior Members and Junior Foreign Affiliates of 755 (from 7116 to 7871). In addition there was a gain of 616 in Student Associates (from 1004 to 1620). Taking account of small losses totaling 5 in the other grades, the net increase was 1366 bringing the total to 9607, the highest figure reached in the history of the Institute except at the end of 1921 when the total was 9850. In part the gain is accounted for by the smaller number lost by suspension

Jan 1, 1937

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By P. D. Merica

ALUMINUM and its alloys have been the subject of much investigation, during recent years, in the course of which the principal features of the constitution of most of the binary alloy systems with aluminum have been determined. Except in the case of a few metals-silicon, bismuth, cadmium, lead, zinc, and tin-an aluminum-rich compound is formed in each binary system, which forms a eutectic with the aluminum or its solid solution with this compound. Thus such compounds as FeAl3, CuAl2, Mg4Al3, and NiAl3 are formed, which are found in aluminum-rich alloys of their respective series as eutectics with the aluminum solid solution. These compounds are, in all cases, hard and brittle and their presence affects profoundly the physical properties of the alloys in which they occur. Within the zinc-aluminum system a compound, Al2Zn3, is formed that decomposes at lower temperatures. Silicon and tin each form a simple eutectiferous series with aluminum; bismuth, lead, and cadmium are only partly miscible in the liquid state with it. The extent of the solubility in aluminum, in solid solution, of these compounds or of the elements themselves, in the case of those series

Jan 7, 1919

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By A. Lucian Walker

SILVER is not only of paramount importance to millions of people as a medium of savings and to other millions as a medium of exchange, but it is also valuable and useful in industry. Mexico continues to be the largest producer of this metal, followed by the United States, Canada, and Peru. The largest consumers are China and India, which normally absorb about two-thirds of the world's mine production, hoarding it as savings. The imports by these countries exert a powerful influence upon the price, yet neither country is on the silver standard. China having abandoned it in 1935 and India in 1893, when the rupee was definitely linked to the pound sterling. Other nations such as Persia, Ethiopia, Mexico, and many of the South American countries either have been on the silver standard or have used silver as their chief circulating medium, and most large nations use it for subsidiary coins, this use accounting for 20 to 30 million ounces annually. The arts and industries have consumed 35 to 40 million ounces each year.

Jan 1, 1937

By C. W. Hall

MINE executives, as a rule, have always been willing to adopt new ideas of operation, or to listen to proposals which might increase the effectiveness of their enterprise, more especially so if they could be shown how definite results might be attained by introducing any conception suggested. In these days of high wages, high cost of supplies, and high taxes, operators are even more inclined to accord consideration to innovations or improvements, and many go so far as to employ men to conduct special investigations and make studies for the purpose of advancing production. Where a man is brought into an organization to do work of an efficiency nature, it often creates resentment among the operative heads because of having their work directly scrutinized, or investigated, and there is a tendency, if not actually to obstruct, to fa.il to cooperate; in which case the investigator is handi-

Jan 1, 1925