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By Charles S. Barrett

This paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstruc-tures. About 1200 exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,' and a number of these have been selected to illustrate the results obtained. prints are also included showing the common types of falsities—to borrow a term from the biological field, the "artifacts." ln brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. In addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains, since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. Specimen Preparation and Photographs Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for these polishing and etching (each successive polish becoming less severe and each etch lighter), since the fina1 etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and 16, the replicas used were of silica, deposited upon polystyrene and floated from the polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1944

By Charles S. Barrett

This paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstruc-tures. About 1200 exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,' and a number of these have been selected to illustrate the results obtained. prints are also included showing the common types of falsities—to borrow a term from the biological field, the "artifacts." ln brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. In addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains, since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. Specimen Preparation and Photographs Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for these polishing and etching (each successive polish becoming less severe and each etch lighter), since the fina1 etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and 16, the replicas used were of silica, deposited upon polystyrene and floated from the polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1944

By E. C. Simmons

Uranium is an incompatible element with respect to the major rock-forming minerals crystallizing from granitic magma, entering instead trace minerals such as zircon. The relationship between the saturation limit (SL) for such a mineral and the bulk distribution coefficient (Do) for U is central to understanding the distribution of U and its availability to late-stage fluids that can form ore deposits directly, or labile U that can be remobilized later. Low SL values imply early crystallization of zircon, but in very small proportions, minimizing Do and maximizing the degree of enrichment of U in late-stage fluids. Thus, granitic rocks with low Zr contents (due to a low saturation limit for zircon) are most likely to evolve U-enriched differentiates; this will be reflected in a high U content of the zircons (but not necessarily high U abundances in whole-rocks). Thus, the ratio of the U content of zircon to the Zr content of the corresponding whole-rock is potentially a very useful parameter in identifying granitic rocks most likely to have U-enriched solutions associated with them. The granitic rocks associated with the U deposits of the Midnite mine area, Washington, have geochemical characteristics that fit the model presented very well. The rocks are very low in Zr (100 ppm) and contain zircons with extremely high U contents (3,000-4,000 ppm).

Jan 1, 1984

By R. T. Gallagher

FOLLOWING recent precedent, the Mineral Industry Education Division opened its first session on Sunday afternoon at the Columbia University Men's Faculty Club with an unexpectedly large attendance. The first session was presided over by the Division Chairman, A. F. Greaves-Walker. The first paper, a preliminary report on college enrollments in mineral technology curricula, by W. B. Plank, though incomplete, pointed to a general over-all reduction of 38 per cent in enrollment in mineral industry curricula. Following that, A. C. Callen's paper elicited many comments. It presented the results of a survey (no direct questions asked) addressed to officials in the mining industry. J. L. Bray spoke on war production drive methods and results and his slides gave visible evidence (and much laughter) of the success of the drive. C. L. Wilson's able presentation covered not so much present status but the future status of accelerated mineral technology programs after the war. The last paper of the first session by Edward Steidle, was handed out in mimeographed form.

Jan 1, 1943

By Donald E. Crowell

In the fall of 1969, ASARCO and Newmont Mining Co. began the design of the 700tpd concentrator at their Black Cloud shaft located near Leadville, Colo. The concentractor would treat by flotation a Pb-Zn-Ag ore containing minor gold values. Flowsheet design was based on laboratory test work performed at the Minerals Research Testing Laboratory of ASARCO. Since the concentrator is located at an elevation of 11,000 ft, cold weather was a major factor in design considerations. The original capacity was designed as 700 tpd but for various reasons an ultimate capacity of 1,000 tpd was desired. This necessitated special consideration in the design of several areas, particularly the grinding circuit. The grinding circuit chosen was a single 9 X 12 ball mill operating in closed circuit with one 20-in. cyclone. The ball mill will operate at low speed and as an overflow type originally. The mill can be speeded up and converted to grate type for handling the larger tonnage when required. Thickeners and filters were oversized and space was left for additional flotation cells in order to handle the increased tonnage in these areas. Pumps were sized so that they could handle the increased tonnage by increasing their speed. Construction began in May 1970; the Black Cloud concentrator went on-stream in April 1791.

Jan 1, 1974

By Horace V. Winchell

The laws here referred to are those which define the status of the prospector for mineral deposits in the soil or beneath it, establish his methods of procedure, protect him in his possession while searching for the subterranean treasures, and give him assurance of title when all required conditions have been fulfilled and valuable minerals discovered. Regulations for the operation of mines and the safety and health of mine employees are likewise subjects of Federal and State legislation, but are not within the scope of the present program. Various features of our present laws will be discussed in detail by able students of the subject, and specific remedies will be proposed for the most glaring defects. It is my purpose to present in this paper a summary review of the reasons why revision is needed and demanded by the great majority of those in daily contact with the industry. Reason Number One The first objection to the continuance of the present law is that it was not planned by its framers and the Congress which passed it to apply to many of the kinds of mineral deposits, nor to the mining conditions, which are controlled by it to-day. In 1866, under the title, "An Act granting the right of way to ditch and canal owners over the public lands, and for other purposes," was surreptitiously smuggled into existence our first mining law (14 Stats. at Large, Chap. 262, p. 251). This law provided that "whenever any person or association of persons claim a vein or lode of quartz or other rock in place, bearing gold, silver, cinnabar or copper, having previously occupied and improved the same according to the local customs or rules of miners in the district where the same is situated," etc., a patent might be granted an certain conditions. This was evidently an Act intended to validate claims already initiated, and to accord Federal recognition to mining locations made in

Jan 1, 1915

By H. W. Paxton, G. M. Pound

A method is outlined for taking into account variation in chemical potential of both components in evaluating capillary effects at growing interfaces. The results are compared with experiment, and seem to be in reasonably good accord for Widman-statten ferrite growing in austenite. ENERY pointed out that during the steady-state growth of phases with a rather small radius of curvature at their advancing edge capillarity cannot be neglected. By proper application of the Laplace equation a correction must be made to the activity gradients down which diffusion occurs. Subsequent workers have concerned themselves with attempts to evaluate specific cases by the use and modification of the principles laid down by Zener.2-5 To solve the problem in its simplest form it is necessary to assume thermodynamic equilibrium at the interface and to select some criterion which will allocate the available free energy between reversible and irreversible processes. Zener chose to assume that the division should be made such that the new phase grew at the maximum rate. Other workers have used the same2,3 or different assumptions, e.g., maximum rate of free-energy dissipation,4 minimum rate of entropy production.5 Li6 has proposed that the "thermokinetic potential" should be a minimum at steady state. The purpose of this presentation is to note that most prior treatments have considered variations due to capillarity only in the chemical potential of the mobile constituent, and that a more consistent treatment must involve a consideration of the variation of chemical potentials of both solute -and sol- vent in a binary system.* As an example, the way in which this arises for ferrite growing from austenite may be illustrated by reference to Fig. l(a). The line OABC shows a typical variation of carbon activity with composition at one atmosphere pressure (at a transformation temperature below A3). In the tip of a growing ferrite plate with a hemi-cylindricab leading edge of radius ?, the pressure due to capillarity is*

Jan 1, 1963

By I. W. Alcorn

The cost of drilling in the past few years of proration and ever decreasing allowables has received increasing thought and study. It seems to parallel the strides made with respect to pumping problems in 1932 and 1933. Low profit margins stimulate the search for economies. Any discussion of slim-hole drilling involves a multitude of abstract values, and the problem can be attacked only by a study of records and rational thinking. In a measure, traditional methods must be studied with a questioning attitude. The words "slim hole" may be somewhat misleading, as the term is entirely relative. For that reason I wish to define it as used in this discussion. On the Gulf Coast, I would define a normal hole as one in which 10 3/4-in. surface casing has been set and below which a 9 7/8-in. hole is dug. With this as a datum, holes of larger diameter below surface would be called "large holes," with 121/4 in. as the "extra large" class and holes of smaller diameter classed in the slim-hole range, 6 1/4 in. representing about the minimum size. The optimum size has not been definitely determined, but the preference is for a program that would call for setting 8 5/8 -in. surface casing and digging a 7 3/4 - in. hole. Different sections of the country might very properly deviate from this practice because of differences in depth, formations, regulations, or other factors. This paper will be confined to a discussion of the drilling of exploratory wells, as the drilling of this class of wells is quite a different problem from that of drilling a proven field, although many of the same considerations apply in both cases, as will be apparent. Although for many years shallow slim-hole and core-test holes of small diameter had been dug, it was not, I believe, until the fall of 1937 that serious consideration was given to its application in drilling wells 7000 ft., 8000 ft. and 9000 ft. deep on the Gulf Coast. This does not mean that nearly all such wells drilled on the Gulf Coast now are of the slim-hole variety, but only that efforts have been aimed in that direction with very encouraging results and there has been a very definite trend to reduce the size of holes, a trend that probably will continue. As to exploration policy, there appear to be two distinct and opposite views. The one usually followed in the past was more or less designed to "shoot the works" on one well. Generally on the Gulf Coast, the depth at which production might be obtained is limited by the drilling equipment and economics. With this thought in mind, wildcat wells are often planned with the idea of carrying the depth to 10,000 It., or even 15,000 ft. All of the possible hazards are anticipated and the general drilling and casing programs are so predicated. Such wells contemplate the drilling of large-diameter holes; the setting of at least one protective string of casing and an extensive coring policy, all of which finally adds up to an expensive well. AS opposed to this general policy is the slim hole. This, on the Gulf Coast, recognizes that new discoveries represent gam-

Jan 1, 1941

By I. W. Alcorn

The cost of drilling in the past few years of proration and ever decreasing allowables has received increasing thought and study. It seems to parallel the strides made with respect to pumping problems in 1932 and 1933. Low profit margins stimulate the search for economies. Any discussion of slim-hole drilling involves a multitude of abstract values, and the problem can be attacked only by a study of records and rational thinking. In a measure, traditional methods must be studied with a questioning attitude. The words "slim hole" may be somewhat misleading, as the term is entirely relative. For that reason I wish to define it as used in this discussion. On the Gulf Coast, I would define a normal hole as one in which 10 3/4-in. surface casing has been set and below which a 9 7/8-in. hole is dug. With this as a datum, holes of larger diameter below surface would be called "large holes," with 121/4 in. as the "extra large" class and holes of smaller diameter classed in the slim-hole range, 6 1/4 in. representing about the minimum size. The optimum size has not been definitely determined, but the preference is for a program that would call for setting 8 5/8 -in. surface casing and digging a 7 3/4 - in. hole. Different sections of the country might very properly deviate from this practice because of differences in depth, formations, regulations, or other factors. This paper will be confined to a discussion of the drilling of exploratory wells, as the drilling of this class of wells is quite a different problem from that of drilling a proven field, although many of the same considerations apply in both cases, as will be apparent. Although for many years shallow slim-hole and core-test holes of small diameter had been dug, it was not, I believe, until the fall of 1937 that serious consideration was given to its application in drilling wells 7000 ft., 8000 ft. and 9000 ft. deep on the Gulf Coast. This does not mean that nearly all such wells drilled on the Gulf Coast now are of the slim-hole variety, but only that efforts have been aimed in that direction with very encouraging results and there has been a very definite trend to reduce the size of holes, a trend that probably will continue. As to exploration policy, there appear to be two distinct and opposite views. The one usually followed in the past was more or less designed to "shoot the works" on one well. Generally on the Gulf Coast, the depth at which production might be obtained is limited by the drilling equipment and economics. With this thought in mind, wildcat wells are often planned with the idea of carrying the depth to 10,000 It., or even 15,000 ft. All of the possible hazards are anticipated and the general drilling and casing programs are so predicated. Such wells contemplate the drilling of large-diameter holes; the setting of at least one protective string of casing and an extensive coring policy, all of which finally adds up to an expensive well. AS opposed to this general policy is the slim hole. This, on the Gulf Coast, recognizes that new discoveries represent gam-

Jan 1, 1941

SIR ROBERT HADFIELD, London, England (written discussion*).-We have in the past known so little about tungsten that an important paper such as Mr. Zay Jeffries contributes is most welcome. I have not much personal knowledge on the subject except as regards combinations of iron with tungsten. I put forward the results of my research on natural alloys in 1903,1 and so far as I know the facts there presented still stand. Singular to say, tungsten added to iron affects the electrical resistance less than any other added element. The following tables taken from research work by myself and Sir William Barrett may be of interest.

Jan 10, 1918

By Persifor Frazer

COMPARATIVE columns expressing the series of rocks of the lower half of the Mesozoic age in this country and in Europe are not yet definitely established. The following represents a co-ordination of the beds in England and Germany,* with a list of materials to be worked in from this country. † * Cotta, " Geologic der Gegenwart." † Section from York to Dillsburg. Report C, 1875; Second Geological Survey of Pennsylvania.

Jan 1, 1877

By Raymond B. Ladoo, C. A. Stokes

This paper summarizes the economic problems of the industrial mineral industries which are essentially different from those of the metals and the fuels. Failure to understand and evaluate such factors as markets, place value, and substitutions of one mineral for another may be disastrous. The engineer should be as responsible for profitable operation as he is for technical efficiency. The Raw Materials Survey of Portland, Oregon, is described.

Jan 2, 1950

By Arthur Crowfoot

INTRODUCTION The principal object of this paper is to present data on the development of the revolving convex round table as a concentrator for the through 0.07-mm. slimes from the ores of the Butte district, although same brief notes on the earliest recorded use of this type of concentrating table in the ore-dressing plants of the Lake Superior region and of the Butte district are also presented. The revolving convex round table belongs to the class of concentrating tables known as film-sizing tables, these tables using the relative transporting power of a film, or thin sheet of water, as it flows over a quiet inclined surface, to separate the minerals of a sorted product.

Jan 8, 1914

By David J. Mack, Chin Bea Kim

The decomposition of the Ni-Zn eutectoid at 56 wt pct Zn was studied by isothermal transformation. Its progress was followed by metallographic, hardness, and X-ray diffraction methods. Three transformation products were found: lamellar pearlite at high temperatures; an intermediate temperature structure; and martensite at the lower temperaCures. No transition structu,ves were found. THE decomposition of the Ni-Zn eutectoid at 56 wt pct Zn was stuadied as part of a long-range program of study on the eutectoid transformation in alloy systems which do not have one or more components which exhibit allotropy. Available information on the Ni-Zn eutectoid transformation is limited to that presented in connection with the determination of the phase dilagram. No systematic studies of the eutectoid were found in the literature, alkhough the microstructures of the Ni-Zn eutectoid were reported by Tamuru.3 X-ray diffraction data exist for the ß, ß1, y , and y1 phases.' EXPERIMENTAL PROCEDURE The eutectoid alloy was prepared from "A" nickel shot and Bunker Hill super-purity zinc (99.998 pct).

Jan 1, 1962

By Charles M. Rolker

It is not my purpose to present a complete description, still less a thorough discussion from a theoretical stand-point, of the Leadville ore-deposits. Hence I have given to this paper the more modest name of " Notes;" since it is little more than a record of observations made three or four years ago, and now published from my original memoranda, with the view of preserving the facts rather than of

Jan 1, 1886

By L. W. Pommier, F. B. Brien

The Rheological properties of pulps are non-Newtonian in character and more than one viscosity parameter is necessary to describe their behavior, therefore, the single term 'apparent viscosity' which has been used in the past may be misleading. The study reported in this paper uses a dimensional analysis based on the Ostwald-de Waele shear stress-rate of shear model for non-Newtonian liquids to develop velocity and resistance equations for falling spheres. An electronic monitoring apparatus was assembled for determining the velocity of metallic bodies as they fall through opaque liquids and suspensions. By means of this apparatus the behavior of the viscosity parameters of the Ostwald-de Waele model and the applicability of the proposed equations were examined for a number of non-Newtonian liquids. The validity of the equations for these liquids was confirmed. Preliminary data collected using solid-liquid suspensions established the validity of the form of the basic equations for these systems. The differential movement of solid particles through solid-liquid pulps and suspensions is very important LO many branches of engineering, such as minerals processing, soil mechanics, ceramic slip processing, oil well drilling-mud technology, materials-handling in pipelines, and many others. There is a dearth of fundamental knowledge on the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. The resistance offered by Newtonian liquids to the movement of free settling spheres is well described for laminar and turbulent conditions by Stokes' and Newton's Laws, respectively. However, problems are encountered when attempts are made to extrapolate these simple relationships into solid liquid suspensions. The rheological properties of pulps are such that they are non-Newtonian in character;'" that is, the applied shearing stress and resulting rate-of-shear are related by non-linear functions, and thus, in the simplest case two viscosity parameters are necessary to describe their rheological properties. For this reason the single term 'apparent viscosity' which has been commonly used to explain the flow resistance of suspensions and non-Newtonian liquids may be misleading. It is realized that a rigorous analysis of the rnechanisms of momentum transport of liquid-solid systems is complex indeed. There are many variables that affect the rheological properties of the systems such as density, size, shape, and surface energy of the suspended solid and density and viscosity of suspending liquid, as well as the solid to liquid ratio. However, it was felt that a useful contribution to the knowledge of the behavior of suspensions could be made by examining the systems in terms of the basic fundamentals of nowNewtonian flow. This has led to the development, by means of dimensional analysis, of velocity and resistance equations, using two viscosity parameters to describe the velocity of penetrating bodies and the flow resistance encountered by these bodies, as they pass through non-Newtonian systems. THEORY In order to examine the effects of the rheological properties of solid-liquid suspensions on the movement of immersed bodies it is appropriate to start with non-Newtonian liquids and develop equations, analogous to those of Stokes and Newton, for laminar and turbulent flow respectively, from which quantitative information may be obtained. Further investigation would then be directed at the complex suspension systems, and the effects of the many variables on the velocity and resistance equations. Liquids are classified on a basis of viscosity which may be defined as the relationship between applied shear stress and resulting rate of shear?-'* Pure single phase liquids composed of small light molecules behave as Newtonian liquids, having a single viscosity parameter since the shearing stress and rate-of-shear are related by a linear function. Bingham plastics are similar but have a yield stress. Of particular importance in our investigation are dilatant (shear thickening) and pseudoplastic (shear thinning) non-Newtonian liquids, with and without yield values.

Jan 1, 1968

MAY began with a general strike of the bituminous and anthracite coal miners in the United States in progress, while in Great Britain about three quarters of a million workers became idle by a lockout, caused by a dispute respecting the question of the rights of management in their shops. The employers opened their shops on May 3 to men wishing to resume work, but few availed themselves of the opportunity. Up to this time the statistics had been showing a little increase in the rate of employment in Great Britain and business conditions were considered to be improving. From Russia came reports that the results of the famine had not been so bad as had been prophesied, which is not to say that they were not grievous. In prognostications such things are habitually overesti-mated. Seeding for the new crop has now begun in Russia, with hopes for better results than last year. However, the general economic situation in Russia steadily becomes worse. We had advices during May to the effect that the Soviet Government had decided to abolish the gold ruble even as a theoretical calculating unit and substitute a "goods index." This idea would be somewhat on the lines of Professor Fisher for stablizing the dollar, and there may be a chance to see how it will work in practice. There was a contradictory report from Russia, however, that it had been decided to revert to the gold basis. This is the more plausible report, for if there be anything to be deduced from economic theory and history the present paper rubles will completely collapse and return to gold basis will ensue simply because the people will refuse to sell their goods on anything else. The civil war in China came to a head during the first week in May when General Wu-Pei-fu crushed the forces of General Chang Tso-lin around Pekin. The victor declared his intention to be to reunite the North and the South and in course of time to arrange for a constitutional convention. We probably do not under-stand the conditions in China, but recent events do not appear to have solved the grave difficulties there, though they may be a step toward it. However, the immediate outlook does not appear good, General Chang having retired to the north and declared the secession of Manchuria and Mongolia.

Jan 6, 1922

E. G. Spilsbury, New York, N. Y.:—Do I understand correctly that the rolls are at first simple cylinders, one longer than the other, and that flanges are subsequently formed on the longer roll as the result of wear only ? Mr. Payne :—The flanges are formed by the wearing of the shorter roll into the other, which is about an inch longer. When the roll-shells are new, the longer one has machined at each end a ridge about 1/8 in. or 0.25 in. higher than the face. These slight projections help to center and steady the rolls, by locating the flanges in advance. Possibly they might be left off at the start; but Mr. Frazee has found it better, in machining the new roll-shells, to turn such small flanges upon the longer one. In his practice the feed-stream is extended a short distance beyond the two ends of the shorter roll-shell. This allows a small amount of crushing to be done between the flange-ftices and the vertical ends of the shorter roll-shell, which prevents any ridges from forming at the ends of the shorter roll-shell.

Jan 1, 1913

By John W. Cahn

The spinodal has long been regarded as a limit beyond which a homogeneous phase could no longer be metastable. But only recently has it become apparent that a phase beyond the spinodal would decompose by simple diffusional clustering mechanism quite different from the nucleation and growth mechanisms encountered for metastable phases. The theory of spinodal decomposition, which is based on the diffusion equation modified by thermodynamic requirements , is phenomenological, and each parameter can be measured by independent thermodynamic or diffusion experiments. The details of the theory have been carefully verified in a number of simple systems. It appears that the spinodal mechanism is commonly encountered in clustering reactions in solids and glasses. HISTORICAL INTRODUCTION The understanding of the earliest stages of precipitation in alloys has been the subject of three prior Institute of Metals Lectures. In 1932 Paul ~erica' reviewed the puzzling evidence that hardening of duralumin is completed before precipitation of CuAlz takes place and suggested that hardening occurs when the copper atoms "assemble in random groups on lattice positions of the duralumin, not of the CuAlz lattice". He called these random groups knots. This modification of his dispersion hardening theory seemed to fit all the facts, but Merica worried that the required diffusion "is just the reverse of what we deem normal; although quite spontaneous, it proceeds uphill, if you please". The reality of Merica's knots was quickly confirmed by Guinier's' and preston's3 X-ray work and these knots are today known as G.P. zones in their honor. Theoretical justification for uphill diffusion was also quickly provided by Becker and Dehlinger~ who noted that the diffusion coefficient could be negative in certain regions of phase diagrams. The boundaries of such regions could be described by a 90-year-old thermodynamic concept first described by ~ibbs' in 1877 as a limit of metastability for fluid phases, which by 1890 had received the name spinodal (see Appendix A). Spinodal in fluids is as old as nucleation theory. Both appear for the first time in the same paper by Gibbs who called the spinodal the limit of metastability. For the first 50 years, nucleation theory was forgotten and the spinodal was extensively treated in every good thermodynamics textbook.81Q The idea was simple and logical and it was accepted as part of a rigorous thermodynamic development of metastable phases, and for a while it was extensively investigated theoretically.

Jan 1, 1969

By Jei Y. Choi, P. G. Shewmon

Using a scratch smoothing technique, the magnitude and the ratio of the surface diffusion coefficients (D,) in two orthogonal directions have been measured on copper for over 100 different surface orientations. Anisotropy was found for all surface orientations except those lying near the (100) and (111); however, these anisotropies were rarely greater than 2.0. The direction of maximum D, appears to coincide with the direction of step edges on any given surface, and if no such steps exist, no anisotropy is found. Thus the jump frequency along a step edge is shown to be faster than the frequency of a jump over the step. The values of Ds and AH for the (100) and the (111) orientations agree quite well with those obtained earlier by the grain boundary grooving technique. It is proven that the directions of maximum and minimum D, (the principal axes) for any surface orientation are known if the perfectly ordered plane corresponding to the given surface orientation possesses a plane of mirror symmetry. Thus the principal axes of D, for orientations lying along the sides of the unit stereo-graphic triangle are always known independent of the extent of thermal disorder or impurity adsorption. The merits and shortcomings of King and Mullins' recently published equations relating Ds to the rate of scratch smoothing are discussed. 1N an earlier paper the authors have reported the variation of the surface diffusion coefficient (Ds) with surface orientation on copper.' In that study Ds was determined from the rate of growth of grain boundary grooves on symmetric bicrystals. This gave values of Ds from 850° to 1070°C in a given direction on each of the six surfaces. It was found that the activation energy for surface diffusion was essentially the same for all six surfaces. The theory developed to explain these data assumed that the free energy of any given type of surface site depends only on the number of nearest neighbors the atom has. This same theory predicted that on any given surface Ds should be independent of direction. The primary aim of this study was to check the validity of this prediction for a wide range of surface orientations on copper. The growth of grain boundary grooves is ideal for studying Ds in a given direction on a given surface over a range of temperatures, because the same specimen can be repolished and used again. However, there is considerable work involved in growing a symmetric bicrystal, and for a survey of Ds in two or more directions on many surface orientations, the technique would be arduous. A better technique appeared to be the scratch method used primarily by Mykura. 2 If a scratch is placed in a surface whose surface tension is independent of orientation, the surface will smooth out in time under the influence of surface tension. To determine D, from this flattening, Blakely and Mykura2 used an approximate solution which was assumed to describe the rate of flattening. Recently King and Mullins3 (hereinafter K and M) have given a more exact analysis of the flattening of an isolated scratch. A second aim of this paper was to check the validity of this newer analysis and compare the values of Ds determined thereby with the values obtained from grain boundary grooving techniques. EXPERIMENTAL PROCEDURE In an effort to work with a particular predetermined surface orientation, light orthogonal scratches

Jan 1, 1963