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By P M. Outhwaite

Everyone present today is especially aware of the need for minerals in this society of ours. The words 'especially aware' were deliberately chosen because this is a meeting of the NZ Branch of The Australasian Institute of Mining and Metallurgy not a dilettante group such as some of our critics. Members of the Australasian Institute of Mining and Metallurgy knew that our great farming industry, our shelter, our transport and our energy supply, are largely dependent on a flow of minerals into this country despite the presence of large coal and natural gas reserves. Flow in was said because New Zealand imports most of its mineral requirements with all the consequential strategic and economic disadvantages. If the above statements are accepted by this gathering it would be a premise fairly stated that New Zealand has a great need to discover and develop minerals.

Jan 1, 1976

By Carl Lemke

SOME of the principal metallurgical difficulties en-countered in the differential flotation of lead-zinc-iron sulfide ores arise from the following causes: The oxidized, or partly-oxidized, condition of one or more of the minerals ; impurities in the minerals them-selves; composition and character of the gangue miner-als; soluble salts in the ore; and unfavorable metal ratios. In many of the ores received at a custom mill there are present appreciable amounts of oxidized' or partly-oxidized minerals, although the ores may be substantially sulfides. Often the ores are not oxidized at all when received but on account of operating condi-tions at the mill it is necessary to stock them for several months before they can be milled, and considerable oxi-dation takes place while they are lying in stock. In most ores received at Midvale, when oxidation is pres-ent, the lead and iron sulfides have been more affected than the zinc sulfide, but with some ores the zinc mineral has also become partly oxidized. Some ores, such as those taken from old mine-dumps or from old stopes, may show very little total oxidation, but the greater part of the valuable minerals has been sufficiently acted upon by oxidation to make the minerals very difficult to float. Ores of this character are among the most difficult the flotation operator has to contend with, be-cause the galena, sphalerite, and pyrite are all sluggish in their behavior in the flotation cells. Only a part of the lead mineral will float in the lead circuit. The re-mainder will lag badly and tend to come up with the zinc or, if badly oxidized, will go -through all the flota-tion circuits into the tailing. The zinc mineral, if it has also been affected by oxidation, will act in a man-ner similar to the lead mineral. A hard pull will be required to float a reasonable percentage of it, and this is likely to bring up so much pyrite that it will be difficult to make a zinc concentrate of commercial grade. If it happens that the zinc mineral has not been no-ticeably affected by oxidation it will tend to float in the lead circuit because a hard pull is also required in that circuit in order to bring up the sluggish galena. When only a fraction of the sulfide minerals has become partly altered, or completely oxidized mineral is present in relatively small quantity, it is usually possible to make reasonably clean concentrates of all three sulfides, that is, lead, zinc and iron concentrates. Most of the oxi-dized and semi-oxidized minerals will go into the tailing and the losses will be proportional to the oxidation.

Jan 4, 1927

By A. H. Balch

A physical elastic seismic model, based on the Peoria oil field was constructed and used to produce multi mode cross-borehole seismic data. Because this was a physical model, it was necessary to deal with a complex wave field consisting of compressional waves, shear waves, and converted waves. The recorded raw data were complex, have no resemblance to the inter-well geology, and were difficult or impossible to interpret. These unintelligible data sets were extensively computer processed. Detailed, accurate, images of the inter-well structure, and reflecting horizons were obtained as a result of this processing. This investigation demonstrates that excellent, accurate images of the inter-well geology can be obtained by skilled seismic cross-well data acquisition and extensive careful computer processing.

Jan 1, 1993

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 William A. Johnson

IT was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomogeneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot he obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yields information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most important types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in a gold-lead

Jan 1, 1942

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 Mehl

IN examining the progress of metallurgical science, the critic must remember that most of our present knowledge of metals and alloys has been accumulated through the needs of industry and commerce rather than through the desire and efforts of a large body of scientists interested primarily in developing a science of metals. The progress of metallurgy, scientifically speaking, has been irregular, and little given to the exhaus-tive exploitation of important scientific fields. The experienced engineer now recognizes the need for the development of the basic science upon which his engineering rests. In addition to the increase in knowledge which results from the normal requirements of industry, a development of the basic science of the behavior of metals and alloys is as desirable in metallurgy as in any other branch of science and engineering. The continued growth of the science of metals-as of every other science-requires studious attention to the principles that underlie the behavior of matter, with the result that knowledge in the several fields of interest should continue to increase. Among the various subjects recognized as important in physical metallurgy few have a wider significance than that of diffusion in solid metals. The phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this, the process of diffu-sion is of first importance practically. The formation of alloys by the annealing of mixed powders, first practiced by Faraday and Stodart81 in 1820 and in more recent years investigated by Masing187,189 and others, has led to the development of special alloys like Carboloy, Vascoloy-Ramet, Genelite, Elcon68, and has recently been applied to the production of noble-metal alloys for electrical contacts"'.

Jan 1, 1936

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 Robert W. Bartlett

Both hydrometallurgical and vapometallurgical processes often involve ores that have been previously ground and size classified. When the valuable mineral is substantially liberated, the chemical reaction is likely to occur on the particle surface and the particle core will shrink as the reaction proceeds. If the chemical reaction products are solid materials then a solid shell, usually porous, will form around the shrinking core. This is known as the core/shell or topochemical reaction model. Using a spherical approximation for the particles, equations have been developed to express the extent of chemical conversion of the particle, depending on which one of the following process or mass transport steps is rate controlling:1 (1) chemical reaction at the particle surface, (2) diffusion through the thickening reaction product shell or (3) mass transport through a boundary layer surrounding the particle. In a previous paper2 these equations were coupled with the Gates -Gaudin-Schuhmann equation 3 4 describing the distribution of particle sizes resulting from comminution of rocks and other brittle solids to develop reaction yield curves expressing the weight fraction of metal or other valuable component of the feed that was chemically converted as a function of residence time. This was done for (a) batch, (b) continuous plug flow and (c) continuous back-mix flow (continuous stirred tank) reactors or process vessels. To make the curves of general rather than special utility, the residence time (average residence time for back-mix reactors) was normalized to a dimensionless time by dividing by the time required to completely chemically convert the largest particle in the feed to reac-

Jan 1, 1972

By George W. Becker, Blair R. Benner, Ronald J. Roman

A computer model for the leaching of oxide copper heaps is developed and verified in laboratory tests. The model can be used to scale-up laboratory test data and to simulate the results of various operating philosophies on heap leaching. The model is applicable to leaching processes where the rate of leaching is controlled by a deficiency of reactant or diffusion of a reactant through the leached rock. Several examples are presented showing the sensitivity of the recovery vs. time curve to the variables in leaching.

Jan 1, 1975

By Leonard Grimshaw

DIFFUSION Of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been consider-able, and includes many reports in foreign languages. This work has recently been well reviewed by Mehl1 and Krynitsky,2 and the reader is referred to their excellent bibliographies.

Jan 1, 1937

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

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