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By N. J. Grant, H. Brunner

This paber is concerned with the determination of equations relating elongation to the amount of shear taking place both along grain boundaries and in slip planes of poly crystalline aggregates during creep. Certain discrepancies with previously used equations are pointed out. Grain boundaries were observed to become serrated during creep, but it is shown that this does not necessarily prevent further grain boundary sliding. Direct obser-vations of subgrain boundary ingration lead to the conclusion that this migration facilitates sliding along serrated grain boundaries. It is bointed out that the state of stress at triple boints is still unknown. MOST of the mechanisms of deformation contributing to elongation are shear processes, such as slip, kinking, grain boundary sliding, and twinning. For quantitative investigations of individual deformation mechanism it is necessary to know the equation which permits the calculation of speci-tnen elongation from measured amounts of shear. This calculated elongation must then be compared with the observed total elongation. The authors' special interest concerned grain boundary sliding during creep. Although this subject has already been investigated quantitatively by McLean,' Rachinger,' and Fazan, Sherby, and Dorn, calculations indicated that none of the equations used thus far to relate shear with elongation were sufficiently well founded. A basic study of this relationship was thus made and the results of this study (which do not entirely agree with those previously used) are presented. Most of the ideas set forth apply not only to grain boundary sliding but to other mechanisms of shear as well. THE SPEAR-ELONGATION RELATIONSHIP Basic Models—The relationship between shear and elongation is trivial in the simplest case of shear, which is shown in Fig. l(a). The vector A; designates the displacement across the shear interface, and Au, and Aut are its components parallel and normal to the tensile direction, respectively. It is evident that the specimen elongation due to shear is equal to the longitudinal component of the shear vector, and it should be noted that the normal component does not contribute to the elongation of the specimen (there are, of course, two normal components in a three-dimensional model). The model shown in Fig. l(b) may be applied to mechanical twinning and to subgrain boundary tnigration. In this case the width (h) of an already existing shear band increases by the migration of an interface, but the shear angle y (angle of mis-orientation in the case of a subgrain boundary) remains constant. The geometrical relationships indicated in Fig. l(b) permit this case to be reduced to the one shown in Fig. l(a). For the resulting elongation A6 we find: where AV/V = fraction of the volume of the specimen swept by migrating interfaces , and 1 = length of specimen. Thus, assuming for example that the angle of mis-orientation is 1 deg, and that P = 45 deg, we find that the specimen elongates 0.87 pct of its length if the entire volume of the specimen is swept once by such a subgrain boundary. An example of deformation by migration of subgrain boundaries is shown in Fig. 2. The specimen shown was repolished after 9.8 pct creep strain and the test then continued for another \ pct. Since the shear vector has, in general, a component normal to the surface, subgrain boundary migration results in the formation of an inclined band delineating the region swept by the subgrain boundary. These inclined bands become clearly visible when observed with oblique illumina-

Jan 1, 1960

By Daniel T. O’Brian

Mineral exploration activities are benefiting from new interpretive techniques which have become economically practical with computers. Government agencies, educational institutions, and industry have each contributed research and development efforts for improving the mathematical analysis and graphical display of exploration data, resulting in operational aids not foreseeable a decade ago. Progress has been worldwide and is expanding rapidly. Books 1-10 are supplementing the periodic literature, at least one abstracting service is now active, 11 and an association has recently been formed to encourage and publicize advances in this field. 12 With the diversity of applications, only partial coverage of the subject can be made at any single symposium. Four of the six papers in this section report on the current state-of-the-art in selected areas of interest: graphics, time-sharing, mathematics, and economic analysis. The remaining two papers are descriptions of advanced statistical techniques for gaining additional information during exploration, and illustrate methods which will become more commonly applied in the future. "Computer Graphics: A New Tool for Exploration and Mining" describes the use of a computer and accessory equipment as an information retrieval device, graphically merging and displaying pertinent information for visual inspection and interpretation. This is a rapid means of studying information which has been pre-stored in a form accessible to the computer. Time-sharing is a means of achieving a comparable rapid response when calculations are being performed. The paper, "Some Applications of Time-Sharing in Mining Geophysics," describes the experience of one company using a time-sharing facility for geophysical computations. Another paper on this subject, stressing mining applications, has recently been published. 13

Jan 1, 1969

THE slag performs two useful functions in open-hearth steel- making. First, it is the means of disposal of all the impurities, save carbon, which are removed from the charge materials in refining the steel, so it must be suited to receiving and retaining as much as possible of undesirable elements with minimum loss of iron and useful alloying elements. Second, the slag serves as a buffer between the flame and the bath and transfers oxygen to the metal at a measured pace contrasted with the violent and difficultly controlled oxidation of the bessemer process. At the same time, the slag is a thermal insulator that limits the rate at which heat can be delivered to the metal from the flame, and a heavy slag blanket thereby serves as a brake on production rates. It has been said with justification that the secret of good steel- making is to make a good slag and the steel will take care of itself. In a broad sense, the subject of slag control includes not only the adjustment of the composition of the slag but also of its relative weight in terms of percentage of the metal-bath weight. The slag is made up essentially of: (1) oxides formed by oxidation of silicon, manganese, phosphorus, and iron in the charge, (2) Si02, MnO, MgO, and other oxides charged as such or introduced incidentally with ores or fluxes or by refractory erosion, and (3) lime charged or fed to the heat to neutralize the "acidic" oxides present (Si02 and P205). Obviously, if practically perfect control were possible over the composition of the charge as well as over the oxidation process during the melting period, both slag weight and composition would be very nearly predetermined; and the control problem would be solved. Unfortunately, only a somewhat imperfect control over these factors is possible, so the operator must begin during the lime boil and continue through the refining period to discover and correct departures from the normal pattern of slag development. To do this as the heat progresses, the first helper must be able to make quick estimates of the composition and physical state of develop-

Jan 1, 1964

By H. C. Goodrich

AT THE Utah Copper mine, steam shovels were first used, in 1906, for the removal of overburden, and in June, 1907 for the mining of ore. Prior to 1907, the ore came from underground development work and from stoping. The use of the steam shovel gradually increased until 1914; since then all material, both overburden and ore, has been loaded by power shovels operating on the various benches of the mine. During FIG. 1.-SCENE OF UTAH COPPER MINE BEFORE OPEN-PIT MINING WAS BEGUN. these 19 years, there has been a great improvement in open-pit mining; largely in the use of equipment having greater capacity and dependableness. The history of the development of mechanical shovels and related equipment, as affecting the Utah Copper Co., would be interesting and would justify considerable space; but of greater interest at this time is the operation of the equipment now in use. The Utah Copper mine is in a great deposit of copper-bearing monzonite, which occurs as a prominent headland of the Oquirrh range of

Jan 9, 1925

By M. Cohen

THERE seems to be a natural urge for the human mind to wonder about the beginning of things. When an explosion occurs, we immediately inquire "what set it off?" If a person contracts a disease, we are likely to ask "how did it happen?" On a much loftier plane, when we reflect about the universe, there is the inevitable question "what, or rather Who, started it all?" In principle, these varied queries have at least one attribute in common: they are attempts, whether earnest or casual, to search out the origin of events in nature. Accordingly, they involve not only scientific, but philosophical and even re1igious matters of deep concern. It is evident that, in a broad sense, the phenomenon of nucleation is enmeshed in this enticing concept of "the beginning", but we must extract the scientific component of the problem for our present purposes. Nucleation, as in the case of phase transformations, is best regarded from the standpoint of kinetics. There are then two main steps, which may come in either order: (a) Experimentally, one attempts to measure the frequency with which transformation centers spring into existence; and (b) theoretically, one seeks a model that will account for this observed birth-rate. Temperature, composition, strain, and prior history are some of the important variables that must be considered both experimentally and theoretically when dealing with nucleation in the solid state. Such interaction of theory and observation is an integral part of science in general, but it is particularly significant in the nucleation problem because the very beginning of a phenomenon invariably occurs on too localized a scale in both space and time to be detected with available techniques. Thus, there is little hope of making direct measurements on the nucleus during its birth or to ascertain the exact nature of the process; one can only infer the details of nucleation from the model whose predicted behavior seems to harmonize best with the measured rate of nucleation and its dependence on known parameters. In the field of solid-state nucleation, both theory and experiment call for much ingenuity, but somehow the conceptual schemes have spawned faster than they can be tested by observation. This is not to say that there are many basically new ideas in modern nucleation theory; rather, as we shall see, it is because the required fine-scale measurements are of immense technical difficulty. Quite likely, some of the nucleation models existent today have survived only because of the latitude permitted by meager data. There is great need to bring theory and experiment into better balance in this important area of physical metallurgy. Although one can

Jan 1, 1959

W. 0. HOTCHKISS,* Madison, Wis.-When we began to do geological field work in the Lake Superior region, we found a correlation in existence, and, as youngsters, accepted all that as settled. Both Mr. Allen and I, since that time, have seen a great many things that were not apparent nor visible to Van Hise, and those who worked with him; we realize now that the correlation was not final and that much remains to be determined concerning geology of the Lake Superior region. My attitude on this matter is that we should not publish an amended correlation as a final thing. We should avoid, in every way possible, foreclosing the minds of those who follow us in working in the geology of this region. As a matter of fact, no correlation can be final at present, because facts and data are accumulating so rapidly that every classification must be immediately modified to fit further observation. Consequently, my attitude in this matter would be, instead of saying that the iron formations of the Lake Superior region are all Middle Huronian, to say that there may be three Huronians-or four or five- we do not know. I believe it is better policy to hold to our present correlation. I do not believe there is any economic benefit to the mining man or the geologist working on problems relating to explorations for iron ore, that cannot be just as well solved by maintaining our present correlation, with a. wholesome idea of our lack of knowledge and the necessity for further detailed work. Then, if any new horizons are discovered in any particular range, the minds of the investigators will not be foreclosed because some one has said that all the iron formation is in the Middle so that there is no use looking elsewhere for it. There is use looking elsewhere, in many cases, as the ore deposits become exhausted.

Jan 1, 1920

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

By Ta M. Li

This article draws freely on the experiences of the engineering and operating staff of P.T. Inco and its parent firm Inco Ltd. In addition, information was derived from papers presented during the recent International Laterite Symposium, held in conjunction with the 1979 AIME Annual Meeting, New Orleans, La., February 19-21. The author wishes to acknowledge all contributors and, in particular, Roy Aitken, president and managing director, P. T. Inco.

Jan 7, 1979

By G. H. Cutter

SAFETY in mining depends on wire rope to as great, if not greater, extent than in any other industry. Sudden failure of a shaft-hoist rope might easily result in death or serious injury to the operators and workmen, extensive damage to expensive equipment, and a loss in production while repairs are being made. A wire rope is only as good as its component parts. It must be made from wire properly drawn and treated. It must be fabricated on machines large enough and capable of imparting the necessary qualities to meet the stringent service conditions. However, unless the fundamental requirement of good ropemaking is recognized, all other operations, no matter how carefully performed, will not impart reliability and quality to the product. This fundamental requirement is steel that is homogeneous, of high resistance to fatigue, and of a type suitable for rope wire. Most wire-rope manufacturers agree that rope wire should be made from acid-open-hearth steel. It is comparatively easy to meet the same physical properties with basic steel, but such properties are only part of the requirements for good wire. It is absolutely necessary, particularly for rope service such as mining, where reliability is essential, that the wire be uniform throughout its entire length. Most manufacturers feel that this highly important requirement is better met by acid-open-hearth steel.

Jan 1, 1936

PROF RICHARD ÅKERMAN Stockholm, Sweden ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France R.A. HADFIELD Sheffield England PROF HANS HOEFER Leoben, Austria PROF HENRI LOUIS LE CHATELIER Paris France M FLORIS OSMOND Paris, France JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia CHARLES D WALCOT Washingtion D.C. PROF DR HERMANN WEDDING Berlin, Germany

Jan 1, 1910

In Mr. Weed's interesting paper, frequent reference is made to the Cananea copper-deposits, which are said to have been so vigorously exploited that they produced 14,000,000 Ib. of copper in 1901. The ore-bodies which yielded this large quantity of metal are described as a product of contact-metamorphism, and in Mr. Weed's genetic classification of such deposits, they receive a place under the sub-heading, "Deposits impregnating and replacing beds of contact-zone."* They are considered by Mr. Weed to represent a special type under this head, and are further classified as: " l. Chalcopyrite deposits: (a) Pyrrhotite ores; (6) Magnetite ores, Cananea type." In condensing much information into a comparatively small space, the presentation of a subject may be so abbreviated as to detract from its clearness. The situation at La Cananea, considering its importance from an economic as well as scientific standpoint, may he worthy of more detailed description. As Mr. Weed rightly remarks, " structural differences are so important, and have SO marked a bearing, not alone on the theory of their genesis, hut also on the working of the deposits and a determination of their value as mines, that they merit a full discussion."† It is my present purpose: (1) to show that it is doubtful whether the copper of La Cananea is mined, except to a limited

Jan 1, 1903

By Thomas T., Read

DESIRABLE as it is to summarize what has been set forth in preceding chapters, the task can only be approached with great hesitation. What follows represents the personal views of the author at the moment of writing, reserving the privilege to change them on more mature reflection or in the light of further evidence. With that reservation they may be stated somewhat as follows. Education for the mineral industries falls into two categories; general education and technical vocational, using the word vocational not in its usual sense but to signify preparation for specific activities, in which sense a law school is a vocational school. Even at the beginning, as indicated in the first chapter, mineral industry education was partly general and, partly technical and that relationship still persists, because technical education requires a firm basis of general education. Our general American system is to provide free public' general education through the twelfth grade, or completion of high-school work, though there are already many technical vocational high schools, and even in a community where nearly all the young people are preparing for entrance to college there will be some who wish to qualify for employment at the end of the high-school course, or even on completing junior high. Our educational system, therefore, has not only to provide education for those who intend to proceed beyond the twelfth grade but also for those who, for a variety of reasons, may wish or be forced to cease full-time education at any level between the first and twelfth grades. This study has been chiefly concerned with the problem of what kind and how much technical education to provide for those who have completed the twelfth grade and who wish to make their living in the mineral industries. The obvious fact that the mineral industries employ all sorts of trained persons,

Jan 1, 1941

By John Wellington Finch

WHAT is an engineering opportunity? To the mining .engineer the natural assumption is that the first requisite 'is a mineral deposit, but, of course, it is not so simple as that. There are at various points on the earth really very great mineral deposits which, on account of geographic location, backwardness of the country, or hostility of its natives, are now, and for a long time to come will be, quite valueless. The mining engineer, and for that matter the civil engineer, is more dependent upon the decisions of capital than upon any other factor in his profession. Ordinarily it is to be assumed that money will go to any place where it is clear that an adequate return upon its investment can be secured, but for many years it has not been safe to depend upon this. ' As already stated, there are many places where local conditions are such that mining is not safe to engage in and there are still other places in which conditions have been so aggravated by the Great War and by the social unrest which has upset the Asiatic region that capital is naturally most reluctant to venture, even when engineering data makes the undertaking appear attractive. It will be evident, I. believe, that there are many factors vital to the success of a mining enterprise in some of the remote countries which we do not have to consider in the United States and which do not, in fact, exist here.

Jan 1, 1924

By John Wellington Finch

THE- impression which the public has of northern Canada is that it is a' vast wilderness of forests; river's, and. lakes, sparsely inhabited by. a few Indians and `containing a few, scattered trading posts of the Hudson Bay Co. This is far from the facts. The building of the Canadian Pacific Railway led to the discovery, in 1883, of the nickel deposits of Sudbury, Ont.; these are the largest known nickel deposits in the world and produce about 90 per cent. of the world's output of nickel. The building of the Temiskaming and Northern Ontario Railway north, from North Bay, to open up farming lands along Lake. Temiskaming, resulted in the discovery and development of the great silver deposits of the Cobalt area, Ontario. Since the discovery of these deposits in 1903 to Dec. 31, .1923, Cobalt has produced a total of ' 327,301,897 oz. of silver, valued at $212,668,434, and paid in. dividends $88,338,185. In 1923 the production of Cobalt amounted to 10,285,247 oz. of silver. Just south of Cobalt, in South Lorrain,. a. new silver district has recently been developed and mills have started production. These deposits are of such extent that 'a branch railroad is under construction from Cobalt to that area. Northwest of Cobalt is the Gowganda silver area which is also a producer of silver ore and is now attracting outside attention. This area is not connected by railroad.

Jan 1, 1924

By PALMER H. TYLER

WHEN the Mid-Continent Section of the A. I. M. E. met at the roof garden dining room of the Tulsa Club on Monday evening, May 13, most of the members present came prepared with a credulity-stretching yarn of some sort or other, gathered from actual experience. Perhaps it was not realized at the time that such anecdotes would eventually burst into print, but while the excellent dinner was appeasing the inner man the word was passed around that informality and spontaneity of expression would characterize the meeting, with the result that the shackles of convention were eventually cast aside and the meeting waxed better and better until the hour grew ,late, and the chairman, L. G. E. Bignell, originator of the idea, brought to a close what was agreed to be a profitable and entertaining evening. The ball was started rolling by Paul Ruedemann of the program committee, who offered the following:

Jan 1, 1929

By George F. Becker

Complexity of Rock-Fractures.—The strains to which rocks have been subjected are manifestly very complex, and it is entirely safe to presume that every possible mode of deformation and rupture is exemplified. The most superficial inspection of any ordinary mountain region is sufficient to assure the observer that the rocks have been pressed, stretched, bent, buckled, twisted, and shorn. The study of torsional rupture cannot fail, therefore, to throw light on geological phenomena. The question is how areas which have been broken in this manner are to be distinguished from those which have yielded to other systems of forces. Phenomena of Joints.—It is well known that a large part of the more homogeneous rocks and some very heterogeneous rocks are intersected by partings often ailed joints. These partings are frequently flat surfaces even when seen in very large exposures, but are sometimes surfaces of moderate, single, or double curvature. Joint, usually occur in groups, in each of which the several partings are parallel to one another, and several such groups often intersect the same rock-mass. In such cases the different systems make large angles with one another. Nearly all students of the subject of jointing have reached the conclusion that joints are faulted surfaces, the dislocations usually being of small amplitude; and this conclusion receives abundant support from the study of thin sections under the microscope. It has thus been shown that much even of what would be regarded in hand specimens as mere slaty cleavage

Jan 1, 1895

By A. C. Boyle

PaGE I. Introduction.........68 II. Location of the District,....... • 70 .. III. Stratigraphy...........73 Description of the Rocks.......73 Triassic Eruptives (Andesite Flows and Tuffs) ....73 Triassic Sediments (Shales and Slates)..75 Areal Geology ............75 Structure...-.......76 Folds............. 76 Faults..........79 Shear ...........80 Intrusives..........81 Alaskite Dike.........81 Andesitic Intrusion.......82 IV. PetrogRaphy of thE Rock Types......83 Andesite Flows.........84 Tuff 8...........84 Andesite Tuff........84 Rhyolite Tuff.....-.......85 Alaskite-Porphyry.......89 Andesite Dike........91 V. Description of the Mines......92 VI. Metalliferous Deposits ........ 95 Character of the Ores...........97 Mineralogy of the Ores.......97 Metallic Minerals.......97 Microscopic Character of the Ores...98 Secondary Enrichment....... 103 Genesis of the Ores ...........104 VII. The Sulphate Deposits.......109 Gypsum ..... HO Anhydrite......... ,... 110 Barite............ 110 Origin. with special reference to Gypsum....111 VIII. Summary.............. 113 IX. BIblYogRaphY.............114

Jan 1, 1915

By Paul M. Tyler

THE farmer pays the phosphate miner! Phosphorus is used in fireworks; goes to battle in military smoke screens, incendiary shells, and tracer bullets; and, in vermin destroying pastes, does its part in the war against insects. A lemon phosphate can be had for a nickel at most soda fountains, and tens of thousands of tons of phosphate rock are mined annually for use in the food industries, chiefly for making monocaleium phosphate baking powder. Sodium phosphate cleaning, washing, and scouring compounds consume substantial quantities: the iron and steel industries buy a few thousand tons yearly to make ferrophosphorus and to balance foundry-iron furnace charges; and even nonferrous metallurgists use a little for phosphor bronze and other alloys. Phosphoric acid, its salts, and diverse other derivatives of this versatile element have countless applications, and industrial outlets are increasing rapidly, especially in the United States. Nevertheless, in this country nearly 90 per cent and in the whole world fully 95 per cent of the phosphate rock consumed is absorbed ultimately in agriculture.

Jan 1, 1938

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

Jan 1, 1892