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By Ruixiang Wang, Jinhui Li, Youjun Xiao, Daoling Xiong, Hao Chen

"Leaching solution prepared from spent battery materials contains large quantities of valuable metals, such as Cu, Ni, Co, Mn and Fe. Therefore, recovery of valuable metals from acidic polymetallic aqueous solutions is of great importance for every plant. In this work, a method is introduced of recovery of Ni, Co and Mn from polymetallic solution prepared by leaching spent battery material. The basic concept includes copper was removed through replacement by iron powder followed by iron precipitation in goethite method. The experimental results show that Cu can be removed 99% at least through replacement by Fe powder, and the removal of Fe can achieve 99% by goethite method. At the same time, the loss of Ni, Co and Mn are about 2%, 3 % and 2%, respectively. The process of differential removal of metals can be selected as the treatment alternative that combines simplicity, efficiency and reliability with low capital and maintenance costs. The purified solution which only contains Ni, Co and Mn can be used to prepare NixCoyMnz ternary system precursor.1 IntroductionNickel and Cobalt are very important metals which are applied in many fields, such as energy material and support material for some new material field. The world demands for such metals is progressively increasing, while raw resources are being depleted and with the constraints raised by the Law and related legislation assigned to protect the environment from hazardous wastes in the world. Nowadays study on reutilization of waste materials has great significance for achieving secondary resources recycling and preventing environmental pollution. There are many hydrometallurgy methods applied for dealing with these wastes, while they usually contain large quantities of valuable metals, such as Cu, Co, Mn and Ni, as well as impurities, such as Fe, Zn, and etc. Therefore, proper treatment of these leaching solutions prior to their discharge is of great importance, so that the contained valuable metals can be recovered.Separation and extraction of metals from leaching solution can use some methods through solvent extraction[l,2], ion exchange[3,4], precipitation with sulfide[ 5] or alkali[ 6] and electrolytic recovery[?]. Among the appropriate treatment alternatives, replacement and differential precipitation is the most attractive treatment that combines simplicity, efficiency and reliability with low capital and maintenance costs."

Jan 1, 2011

By A. J. MacRae

Metallurgical furnaces are made up of complex multi-component systems that must function either together or in parallel for safe, and reliable operation. Thermal expansion of single material components experience induced stresses during heating and cooling, which can lead to cracking or failure. Multi component elements and systems can experience significant thermally induced stresses during both steady state and transient temperature conditions. Examples pertaining to temperature effects on refractory, copper cooling blocks, furnace shells, and complete systems will be discussed. The purpose of the paper is to highlight how stresses and strains are developed due to differential thermal expansion.

Jan 1, 2015

By Jürg Künzle

Underground construction is a matter of dealing with the inherent uncertainty of subsurface geology. If the encountered conditions are less favorable than the expected ones, the execution of excavation, support, ground treatment or lining works is likely to require more or different efforts than anticipated, thereby delaying the works and increasing the costs. The 2019 first edition of the FIDIC Emerald Book model contract (FEB) addresses many of the issues to which underground works give rise, including those related to differing site conditions (DSC). This paper examines how under the FEB disputes arising from or in connection with DSC could or should be avoided.

Jun 13, 2021

By AIME AIME

AT a recent meeting of the Utah Section. A.I.M.E., P. D. Nielson, general plant superintendent of the new Geneva steel plant at Provo, Utah, spoke on "General Operations of the Geneva Plant." Mr. Nielson explained that the plant was located at Provo, Utah, on account of railroad facilities, the proximity of coal, iron, and limestone, and the nearness of water for operating the plant. Water probably was the most important item in making the decision.

Jan 1, 1944

By Orlando Oliveros

The Los Bronces Mine and Concentrator, one of the three operating units of Compania Minera Disputada de Las Condes S.A. (an Exxon Minerals Co. affiliate), is located in the high Andes of East-Central Chile approximately 70 kilometers northeast of Santiago at an elevation of 3,650 meters above sea level. (Figure 1). Santiago, the capital city of Chile, is located at an elevation of about 500 meters above sea level and enjoys a very mild climate, similar to some areas of California. At the mine site, however, extremely heavy winter conditions prevail occasionally, with very heavy snow and the resulting snow avalanches endangering installations and people. At the same time, ideal skiing conditions are found at the nearby ski resort of Portillo and Farellones. Mount Aconcagua, the highest mountain in the western hemisphere is only about 55 kilometers further to the northeast of the Los Bronces mine.

Jan 1, 1983

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By A. A. Shirzadi, E. R. Wallach

"Liquid gallium has been used successfully to modify/remove the surface oxides prior to diffusion bonding similar and dissimilar nickel-base superalloys. Using this approach, bonds in nickel-base superalloys with ""virtually invisible interfaces"" were produced, and the compositions in the bond region were very close to those of the bulk alloys. Room temperature tensile and bend tests showed no preferentially failure at the bond lines. Creep tests on samples made between two different Inconel alloys also showed failure away from the joint, i.e. in the parent metal of the Inconel alloy with lower creep resistance. The high temperature lifetimes of these samples were as long as those of the unbounded Inconel, confirming that the joining approach has no adverse effect on the nickel-base superalloys being joined."

Jan 1, 2006

By K. C. Marsden, B. Pesic

"Interest in the efficient production and recycling of rare earth elements has increased in recent years along with the prices of these elements. The molten LiCl-KCl eutectic is one ionic solvent which can be utilized for these purposes. The LiCl-KCl eutectic has also been selected as the electrolyte for focused research for advanced pyrochemical recycling processes for used nuclear fuel in several nations. Rare earth elements are fission products with notable neutron absorption characteristics, and thorough understanding of the properties and behavior of these elements is critical to their successful partition from the electrochemically-similar actinide elements. The number of research papers investigating individual rare earth elements has greatly expanded in the approximately 35 years since the last review. These research papers are presented in a variety of languages and technical formats, making data difficult to compare, and are sometimes contradictory. A review and summary of diffusion properties of rare earths in LiCl-KCl eutectic was performed, and the data translated to a common format for evaluation. INTRODUCTIONThe rare earth elements have experienced growing importance in recent decades due to their application in high technology, including optical lenses, lasers, high-temperature superconductors, improved alloys, high energy-density batteries, and powerful magnets for compact electronic devices. Their historic production methods and uses are detailed in several texts (Hampel 1971; Bautista &Jackson 1992; Gupta & Krishnamurthy 2005). A s the p rice o f these e lements has r isen in r ecent years, so has interest in their efficient production and possible recycling options. Rare earth oxides are concentrated through hydrometallurgical techniques, but the high thermochemical stability of their oxides precludes production of rare earth metals in aqueous systems. However, the wide electrochemical window and better control of pO2- in fused salt systems allows the production of these reactive metals from their halides or oxides. The high ionic conductivity and diffusivity of the molten ionic electrolyte allow high currents with limited resistive losses (Fray 1980). Electrolytic methods in fused salts are commonly adopted for the production of bulk rare earths in a variety of molten salt systems. Fluorides are sometimes proposed for oxide electrowinning processes due to ability to dissolve the rare earth oxide, reduced hygroscopic behavior, and the wider electrochemical separation between O2 and halide gas evolution (Mohan Das, Damodaran et al. 1988; Gibilaro, Pivato et al. 2011). However, in most electrolytic production processes, such as that for mischmetal, the rare earth oxides are converted to chloride prior to electrolysis in a chloride bath (Gschneidner Jr. & Eyring 1978; Sharma 1987). Of the chlorides, the LiCl-KCl eutectic is one specific medium in which metal production and production-related investigations have been conducted (Gschneidner J r. & Eyring 1978; Driscoll & Fray 1993). L iCl-KCl eutectic has the advantages o f h igh conductivity, but relatively low viscosity and operating temperature. The low operating temperature allows simpler design, with reduced energy consumption, salt volatility and cell corrosion."

Jan 1, 2012

By Lev Levin, Sergei Lesokhin

"The formation of titanium carbide during hot filament assisted carburizing of NiTi alloy was investigated. Phase content and morphology of the diffusion zone were examined by X-ray diffraction, X-ray microanalysis, SEM, and Auger electron spectroscopy. The growth of stable and adherent TiC film was observed. A non-planarity of interphase boundary was noticed. The applicability of the chemical diffusion approach to the analysis of the experimentally observed interface instability is discussed. A criterion, taking into account the influence of growth stresses on the stability of the flat interface, is developed by means of linear perturbation analysis.Introduction.Equiatomic intermetallic NiTi belongs to a class of materials exhibiting the shape-memory effect. The unusual property of this compound promotes its application in many fields, from aerospace technologies to medicine. The relatively high ductility ofNiTi also permits its use as a matrix material in metal-ceramic composites. The objective of this work was to investigate the possible incorporation of a ceramic material (titanium carbide) into NiTi by gas carburizing.Free energy calculations indicate the potential to obtain TiC by carburizing Ni-Ti binary phases. The main obstacle to such a process is the high affinity of titanium to oxygen. At moderate temperatures the formation of TiC is preferable to titanium oxidation only if the partial pressure of oxygen is extremely low [1]. This problem was overcome in this work by the use of hot filament assisted gas carburizing. Due to chemical reactions occurring near the hot filament, the gas mixture, initially consisting of methane and molecular hydrogen, was enriched by atomic hydrogen [2], drastically decreasing the content of free oxygen in the carburizing atmosphere.The second part of this article concerns the theoretical analysis of reasons that lead to the development of the experimentally observed morphology of the diffusion zone. In particular, the influence of the growth stresses on the morphology of an interphase boundary is investigated."

Jan 1, 1996

By F. Keller, R. H. Brown

BECAUSE of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1,2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. hot only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating I exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of *417S-T, 17S-T and 24S-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in z4S alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential dif-erence between the core and coating may be less than 0.16 volt, depending upon the thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24S-T, two are generally used; namely, the metallographic and the solution potential method.3 METALLOGRAPHIC METHODS Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24S-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By L. S. Darken

THE manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBSERVATIONS RECORDED IN LITERATURE An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notable uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,1 by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. As an example of a yet more

Jan 1, 1942

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments, and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table 1 are reported the compositions of the core and cladding alloy for the material used for the experiments. [ ] In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion.1-7 Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R301 varies with the gauge, as shown in Table 2, several gauges were investigated. [ ] MATERIAL AND PROCEDURE The material used was sheet of the following gauges: 0.025, 0.040, 0.064, 0.102, 0.170. Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: 910°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After 200 min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1945

By Marie L. V. Gayler

WITHOUT diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange-e.g., of diffusion-is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult-if possible to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, ßFeSi is formed in the solid as the result of the reaction aFeSi + Al?ß FeSi. The particles of aFeSi become sur¬rounded with a reaction ring of ßßFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of ßFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Robert W. Bartlett

Biooxidation of an ore heap containing only a few percent of sulfide minerals requires insertion of a very large amount of oxygen either by natural air convection, forced air ventilation or gaseous diffusion. While shallow heaps, those with lateral distances much greater than their height, are of great interest for many heaped ore processing operations, natural convection is often ineffective for oxidizing them because of inadequate lateral flow into the heap's interior. Oxygen can diffuse into a shallow heap from its upper, horizontal surface in contact with air. Oxygen diffuses through the air-filled void space within the heap, driven by the oxygen concentration gradient resulting from internal oxygen depletion caused by mineral oxidation. Oxygen diffusion, coupled with the chemical reaction kinetics oxidizing the sulfide minerals, is analyzed for conditions of rapid mineral oxidation kinetics, requiring small mineral grain sizes, and for typical ore heap biooxidation parameters. Practical limits on heap heights are presented for effective biooxidation of the sulfide minerals within times of interest for heap biooxidation of refractory sulfide gold ores, one to three years.

Jan 1, 1995

By R. M. Brick

THE Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic prob-lems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segrega-tion. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute con-centration, with a resultant normal segregation or coring effect during freezing. Theoretically, diffusion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions alumimum-copper alloys segregate inversely and aluminum-magnesium alloys segre-gate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By A. A. Smith

THE application of indium to bearings was first advocated by C. F. Smart1 in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. METHOD Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium was deposited and diffusion was carried out at 150°C. for a period of 500 hr. in a thermostatically con- trolled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro- graphically and chemically-the spectro- graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. Also, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at l20°C. for a period of 200 hours.

Jan 1, 1944

By William A. Johnson

THE mathematical analysis of diffusion curves in solid metals is Carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. EXPERIMENTAL PROCEDURE If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By E. O. Kirkendall

THE investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,' particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize; it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosenhain,2.3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,7 and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,' and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. EXPERIMENTAL PROCEDURE This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ±3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 34 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photo-micrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 3a hr. at 300°C. It was then etched in 25

Jan 1, 1942

By Samuel Hoyt

THIS paper gives a brief description of an investigation made several years ago on the diffusion of zinc into copper. The material for that study was furnished in the form of thin copper strips coated with zinc. The result was required rather quickly and at not too great an expense, and especially information was desired as to the rate at which zinc would diffuse from the zinc coating into the copper and the temperature at which the operation should be carried out. A study of the requirements of this problem indicated that the solution might be secured by means of six determinations. This is the smallest number that will give the information desired and, at the same time, furnish checks on the accuracy of the determinations which justify an abbreviated experimental program. This does not count a preliminary test which was designed to give some idea of the correct temperature to use. The minimum number of temperatures that can be used is two. Knowing the rates of diffusion of zinc into copper at two properly chosen temperatures, it is possible to calculate the rate for any other temperature, and also to check the accuracy of the determination by means of the heat of diffusion, which is calculated from the effect of temperature on the rate of diffusion. The minimum number of determinations at any one temperature is three. The amount of diffusion which occurs at a fixed temperature is definitely related to the time of diffusion, so that by determining the amount of diffusion for three different time intervals, this relationship may be established and possibly a check on the accuracy may be secured. This accounts for the six determinations or experiments, and suggests the logical plan of the work. The check used here is not generally applicable to diffusion phenomena, but it seems to hold closely enough for the limited amount of diffusion in this investigation to justify its use.

Jan 1, 1928

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948