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By R. V. Norris

1. INTRODUCTION. THE anthracite coal trade, with a shipment averaging about 70,000,000 tons per year, differs essentially from other coal business, in the fact that the larger sizes, comprising about 65 per cent. of the total, are used almost exclusively for domestic purposes, principally during the winter months; and that for proper combustion close-sizing is imperative, so that eight sizes are made; broken, egg, stove, and nut, known as prepared sizes, and pea, buckwheat, rice, and barley, known as steam sizes. These sizes are made in the regular course of preparation, and but little variation in the natural percentage of each is practicable. Thus it is necessary either to work the collieries intermittently, or to dispose of all the varying sizes in their fixed proportions. Unfortunately, the market does not at all times absorb the coal in proper proportions, and rather than interfere with the regular operation of the mines it has been found economical to provide storage for the excess. While the cellars of the consumers are the great storage-plants of the country, this capacity is not under the control of the trade, except so far as reduced prices during the spring and summer months may tempt the use of this reserve. The same remark applies but with less force to the retail yards, which,, though usually small, store in the aggregate a large amount of anthracite. While every effort is made to utilize to the utmost the individual storage-capacity of the country, there still remains the necessity for taking care of the irregularities of the market by the construction of storage-plants under the direct control of the producers. Such plants are usually the property of the railroads, and are situated at points most convenient from a traffic stand-point.

Jun 1, 1911

By R. L. Templin

THE increasing use of aluminum and its alloys in commercial fields has demanded a better understanding of their machining properties. This fact is exemplified by problems that have arisen in the automotive and airplane industries, but many in other fields might be cited. As pure aluminum and its alloys in their various commercial conditions show appreciable differences in their machining properties, it is not surprising that quite divergent solutions have been offered for the machining problems encountered. However, if the fundamental requirements of the most suitable cutting tools for these metals are understood, these machining problems lend themselves more readily to satisfactory solutions. Since the machining of free cutting brass and mild steel is understood by most persons accustomed to working these metals, it may serve our purpose better to first make a general comparison of the tools more commonly used in machining these metals with the tools most suitable for machining aluminum, then proceed to a more specific discussion of the individual tools. COMPARISON OF CUTTING TOOLS Cutting tools commonly used for machining free cutting brass usually have little, if any, top and side rake; they are ground on a medium to coarse abrasive wheel and used without any cutting compound or with a cutting compound that has a paraffin base. Those ordinarily used for steel have some top and side rake, are usually ground on a medium to fine abrasive wheel, and are often used with soluble-oil cutting compounds. The proper tools for aluminum and its alloys should have appreciably more side and top rake than the tools for cutting steel; should have very keen edges obtained by grinding with fine or very fine abrasive wheels supplemented in many cases by hand stoning with an oil-stone; and should be used with suitable cutting compounds whenever possible. In many cases, tools suitable for machining aluminum and its alloys are not appreciably different from tools commonly used for cutting hardwoods. The front clearance of a tool most suitable for machining aluminum and its alloys should be about 6°, the top rake from 30° to 50°, making the total angle of the cutting edge of the tool from 35° to 55°. A side

Jan 1, 1928

By E. I. Larsen, A. S. Doty, F. R. Hensel

The alloy under discussion is a Pig. I shows results of heat-treating tests nickel-silicon bronze and is one of many on two typical nickel-silicon bronze castings age-hardening or precipitation-hardening of the type on which the observations were copper-base alloys. The hardening constituent is a nickel-silicon compound.l The quenching temperature necessary to produce hardening by a subsequent aging treatment is a function of the composition and extends from about 700°C. to 950°C.; the aging temperature range extends from 4000 to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of: 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Sj: balance. comer. made. A quenching temperature of 750°C. produces almost as high a hardness on subsequent aging as do quenching temperatures of 850' and 900°C. Several foundries have spent years of active and intelligent effort in trying to control the casting and heat-treating variables of nickel-silicon bronzes and finally gave up the attempts because of the inconsistencies of results.2 This undesirable characteristic was not manifest in the ultimate hardness or conductivity but primarily in tensile strength and ductility, as shown in Table I. The variation in tensile properties was often much greater than that existing on the alloys

Jan 1, 1941

By A. S. Doty, E. I. Larsen, F. R. Hensel

The alloy under discussion is a Pig. I shows results of heat-treating tests nickel-silicon bronze and is one of many on two typical nickel-silicon bronze castings age-hardening or precipitation-hardening of the type on which the observations were copper-base alloys. The hardening constituent is a nickel-silicon compound.l The quenching temperature necessary to produce hardening by a subsequent aging treatment is a function of the composition and extends from about 700°C. to 950°C.; the aging temperature range extends from 4000 to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of: 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Sj: balance. comer. made. A quenching temperature of 750°C. produces almost as high a hardness on subsequent aging as do quenching temperatures of 850' and 900°C. Several foundries have spent years of active and intelligent effort in trying to control the casting and heat-treating variables of nickel-silicon bronzes and finally gave up the attempts because of the inconsistencies of results.2 This undesirable characteristic was not manifest in the ultimate hardness or conductivity but primarily in tensile strength and ductility, as shown in Table I. The variation in tensile properties was often much greater than that existing on the alloys

Jan 1, 1941

By John W. Weeton, Donald W. Petrasek

Relatively few metal-metal systems exist that would permit the creation of fiber-metal composites consisting of mutually insoluble constituents. It is anticipated that most high strength-to-weight ratio and high -temperature fiber composites ultimately to be produced will utilize high-strength fibers embedded in a highly alloyed matrix. An investigation was conducted to determine the effect of alloying on the tensile Properties and micro-structure of tungsten-fibey-reinforced composites. Composites were made of tungsten fibers infiltrated with copper binary alloys that contain elements of varying solubility in tungsten. Room-temperature tensile tests were made on the composites, and a metallographic study of the microstructure of the fiber-metal-matrix interfaces was conducted. It was shown that, as the depth of penetration of some alloying elements into the fiber increased, a decrease in both tensile strength and ductility of the composite results. A notch effect, due to the formation of a brittle alloy zone with the tungsten fiber, was observed and gave rise to greater reductions in tensile properties and ductility behavior than would be Predicted by a law-of-mixture relation alone. In recent years, investigators have considered combining fibrous materials with relatively weak binder materials. The interest in fiber-reinforced composites results from the fact that fibers or wires may be exceedingly strong and exhibit mechanical properties superior to those of the bulk materials from which they are derived. For example, tungsten wires drawn to less than 1 mil in diameter may have strengths of over 600,000 psi,' while steel wires ranging from 10 to 3 mils in diameter may have strengths of the order of 300,000 to over 600,000 psi.2 Both metallic and ceramic whiskers are known to have very high strengths. For example, iron whiskers have been shown to have strengths of 1.9 million psi3 and sapphire whiskers have been reported to have strengths of the order of 1.7 million psi.4 If all or part of the strengths of such fibers could be retained, subsequent to the incorporation of the fibers in an engineering material, a superior material could result. In previous work done at the Lewis Research Center, McDanels, Jech, and weeton5 demonstrated the feasibility of fabricating metal-fiber—metal-matrix composites that utilized the full strengths of the fiber and matrix materials. Tungsten fibers were combined with a copper matrix by a liquid-infiltration method such that the tungsten fibers were uniaxially oriented parallel to the tensile axis of the composite. A linear relation was established that related the tensile strength of the composite with the volume percent of the fibers. Mutually insoluble constituents were selected for the study so that the strength of the composite could be quantitatively related to the strength of the individual constituents. The fact that there are only a few metals that are mutually insoluble with tungsten, e.g., copper, silver, gold, and zinc, and that these either have low melting points, high vapor pressures, or poor oxidation resistance, makes it necessary to utilize other metals that are soluble in tungsten, where high-temperature applications are ultimately contemplated. It was anticipated that, for most practical fiber-reinforced composite materials, it would be necessary to use a fiber and metallic matrix that would have varying degrees of solubility for each other. A logical extension of the earlier work was thus felt to be a study that would determine the effects of elements that had mutual solubility with the tungsten. Numerous investigators have found that tungsten fibers may be damaged by thermal treatments or contamination of the surface of the fiber by alloying elements.6-10 On the other hand, surface treatments may improve the strength of such fibers."-" Relatively little work with composites containing tungsten fibers have been reported. The work of parikh14 has shown that kinked, short-length tungsten, steel, and molybdenum fibers could str'engthen such matrices as silver, gold, and copper. Some of the combinations of fibers and matrices studied by

Jan 1, 1964

By G. F. Comstock

The subject of transverse fissures in steel rails has been discussed very thoroughly in recent years from various points of view and the final opinions expressed may be roughly classified into two groups: That these fissures are the result merely of fatigue of the steel and are independent of the quality of the metal. That the quality of the metal and the mill practice must have something to do with them. The first point of view was most ably and logically presented by J. E. Howard,' and in the discussion of this paper, as well as in several other preceding publications, Dr. P. H. Dudley, Consulting Engineer of the New York Central Lines, has strongly defended the other opinion.2 The steel makers of the country have naturally rallied under Mr. Howard's banner, hoping to place the entire blame for these failures upon the railroads with their high wheel-loads, hard steel, heavy traffic, and sometimes inferior road-bed; while the railroad men, on the other hand, have been busy accumulating statistics and records in the effort to find an actual reason in the rails themselves that would account for the seemingly haphazard occurrence of transverse fissures under varying conditions and at widely separated points. The view that these fissures were due merely to normal fatigue under alternating stresses seemed most reasonable to the writer until quite recently, because from work done in this laboratory, as well as the work of other investigators, of the problem, no structural differences, in the vast majority of cases, were found between metal at the nuclei of transverse fissures and metal at similar positions in the same rails or in other rails that had not developed fissures. Within the last year or two, however, since the method of etching polished sections for the microscope with a oupric chloride solution has been tried systematically on lengthwise sections, passing through the nuclei of transverse fissures, evidence

Jan 1, 1920

By T. A. Rickard

The interior of West Australia is an arid table-land, elevated 1400 feet above the sea. This plateau is flanked to the south by the Tertiary limestones which fringe the Great Australian Bight. It is bordered northward by the Carboniferous beds of the Fitzroy river and westward by the granite of the Darling hills, while to the cast this wide area, about 900 miles square, slopes downward imperceptibly into an undulating plain of sand, which stretches with dismal persistence across the boundary of South Australia. The waters of the ocean receded from this tract of land long ago; it is probably the oldest landsurface on the globe, and represents the basal wreck of a much larger continent. Fig. 1 is a map of this region. The Coolgardie and Kalgoorlie gold-fields are situated in the southwestern part of the region. The rock-formation consists of granite penetrated by diorites and andesites. The latter are occasionally associated with tuff's, which have been readily mistaken for sedimentaries. There are no fossil-bearing rocks, such as would afford a datum-line from which to measure the relative geological age of the prevailing formation. On the extreme edges of the mining territory there are, it is true, remnants of sand-rock which are considered identical with the " Desert Sandstone " of Queensland, determined by Daintree to be of Mesozoic age. But even this formation has evidently been laid down so long subsequent to the underlying rocks that it serves merely to emphasize their much greater antiquity. In their characteristics and in their relations to each other, the granite and the diorite of the Coolgardie region appear to me much to resemble the Laurentian granite and the Huronian

Jan 1, 1899

By AIME AIME

SECTION DELEGATES were given an opportunity to see how the machinery of Institute administration functions, on Tuesday evening, Feb. 16, when they were the' guests at the regular monthly meeting of the Directors. Of the new board of 25 members, 19 were present at the meeting, including directors from Seattle, Los Angeles, Wyoming, Oklahoma, Chicago and Pitts-burgh, the new junior past-president from Jerome, Ariz., and the new president from .Washington, D. C. The complete list of the 72 in attendance at the dinner,: held in the main dining room of the Engineers' Club, which pre-ceded the general session of the Directors'. meeting, follows:

Jan 1, 1932

By Otto Henry

THE purpose of this investigation was to determine the equilibrium diagram of the lithium-magnesium pair as a first step in studying the possible usefulness of these alloys as ultra-light structural materials. REVIEW OF THE LITERATURE The behavior of lithium towards magnesium was first investigated by Masing and Tammann.(I)? In order to prevent oxidation the alloys were made in iron tubes under an atmosphere of hydrogen; temperatures were measured with a glass-protected thermocouple. These investigators found that lithium and magnesium form two series of solid solutions separated by a miscibility gap between 85 and 95 per cent magnesium; that the alloys with 81 and 95 per cent magnesium showed a homogeneous structure under microscopic examination, while the alloy with 89 per cent magnesium contained two distinguishable crystallites; that the curve indicating the beginning of crystallization rises from the melting point of lithium to that of magnesium; and that no compounds of lithium and magnesium are formed. The equilibrium diagram was not plotted because no definite data were obtained for determining the solidus and the posi-tion of the miscibility gap in the solid state. The difficulties encountered in this investigation were: (1) that it was necessary to heat them as high as the melting point of magnesium in order to obtain homogeneous melts; at such temperatures the alloys attacked the glass protecting the thermo-couple; and (2) that at temperatures above 400° C. the lithium united

Jan 1, 1934

By F. Twyman, D. M. Smith

THOSE chemists (they are still greatly in the minority) who use the spectroscope, use it very often, and find it almost indispensable. As a means of detecting minute quantities of the metals it is unrivalled. A metal can be readily distinguished in the presence of any other element, compound, or mixture without the necessity of separation. The qualitative analysis of the metallic constituents of a substance, which the spectroscope gives so easily, is a sure basis for planning a chemical analysis. As the determination of each element proceeds the purity of precipitates may be checked as often as desired. If, possessing these advantages, the spectroscope has been neglected in general chemistry, it is not surprising that it was neglected in metallurgical chemistry; for many of the impurities which are of industrial interest, even when they are present in a metal or alloy in small quantities, are not then always easily detected by the examination of their visible spectrum. The history of the development of the art has been given in Bureau of Standards Scientific Paper No. 444.

Jan 1, 1928

THE refining period of an open-hearth heat blends imperceptibly into the finishing period, during which final adjustments are made in slag composition, in bath action and temperature, and in composition of the steel, in order to prepare it for casting into ingots. Operations must be governed by the consideration that alterations in the character of the heat during the finishing period must be held to a minimum. In a broad sense, the finishing and deoxidation period of a heat may be said to begin when the action of the last ore addition has ceased, and to end when the teeming of the ingots is completed. INGOT STRUCTURES A survey of the relative advantages and disadvantages of different types of ingot structure is required because deoxidation treatments during the finishing period control the amount of gas evolved during solidification and consequently determine the type of ingot structure. Four classes of ingots are recognized, depending upon the degree of deoxidation to which the steel has been subjected. These types are killed, semikilled, capped, and rimmed; typical examples of their structures are represented by ingots 1, 2, 5, and 7, respectively, of Fig 9-1. The actual ingots from which these cross sections were sketched were all poured to the same height (indicated by the dotted lines) in the same type and size of bottle-top molds. The eight drawings of the figure represent selected types of ingot structure in a continuous series from "dead killed" to "wild," resulting from variations in the total quantity of gas evolved, from none at all to copious amounts, during solidification of the steel in the mold. Killed and semikilled steels are adjacent at the "quiescent" end of the ingot structure series where only small amounts of gas are evolved. The term "quiescent" describes the action of the molten metal during and subsequent to the teeming of killed and semikilled steels. Capped and rimmed steels are adjacent at the

Jan 1, 1951

CHARGING of an open-hearth heat is begun as soon as possible after the previous heat has been tapped. Ordinarily, about 40 min is required to drain and dress the furnace hearth, make up the taphole, and perform routine repairs of the banks. Repairs to the upper back wall and to the front wall and jambs can ordinarily be done while the first scrap charge is being heated and are therefore allowed to wait in order to save furnace time. Any major repairs required on the hearth or other parts of the furnace necessitate longer delays because such repairs must be made while the furnace is empty. Although charging practice varies considerably in detail with the type and proportions of scrap and iron used, many factors are common to all varieties of charge. Such general considerations are dealt with first. CHARGING EQUIPMENT AND STOCK HANDLING The physical equipment available for loading and weighing the stock, transporting it to the furnace, and charging it, may have a major effect on charging practice. Limestone, scrap, and all other solid melting stock are charged mechanically by means of equipment illustrated in Fig 2-1. The charging of hot metal is shown in- the background of this figure. Mechanical equipment and plant layout for stock handling are described in Chapter 1. It is generally desirable to charge the scrap about as fast as the physical volume can be put into the furnace. Charging scrap that is too heavy or adding the charge too rapidly (less than 45 min) may be detrimental to melting rate because of excessive chilling of the entire furnace system and also because of poor conduction of heat to the lower layers in the furnace; but the more common problem is the reverse one of charging light scrap fast enough to maintain a normal heat time. A limiting factor may be the height to which the scrap may he piled in the fur-

Jan 1, 1964

By R. F. Yap, N. Arbiter, C. C. Harris

A fully-instrumented driving mechanism has been constructed to study the power, aerating and solid suspension characteristics of several laboratory flotation machines. Machines operating over normal flotation speed ranges give substantially constant power numbers in liquid systems indicating that they operate close to fully baffled turbulent flow conditions. Owing to lack of geometrical scaling, power numbers for different sizes of cells of the same make are different. Even larger differences occur between cells of different manufacturers. For a given impeller, varying the tank size did not significantly affect the power consumption. Tank geometry and baffling has a slight effect on power consumption with shrouded impellers. For a given impeller speed, suspension height decreases while power increases with increasing mass of solids in suspension. While power consumption is hardly affected by particle size and clearance between the impeller and tank bottom, the suspension height significantly increases as clearance increases and as particle size decreases. Aeration was found to affect not only power but also the suspension characteristics of the machine. For closely sized particles, drastic sedimentation occurred when a critical value of the air flow number was exceeded. The critical air flow number decreased with increasing particle size. This effect was less marked with a wide particle size range. The self-aerating capacity of flotation machines increases with cell size at a given speed for the same impeller-shroud system, but decreases in the presence of frother and solids. Equations have been established for correlating all of the studied variables. Data taken from the literature were also correlated with these equations. The modern mechanical flotation machine has, over a period of 60 years, displaced other designs to become the dominant type. Once the correct chemical environmental conditions have been established, the major requirement, selective mineral-air adherence, is essentially a function of two operating variables — impeller speed and air rate. The special nature of this dependence is such that in the same apparatus, but under different operating conditions, adherence can be either prevented or destroyed. Another aspect of this observation is that flotation machines though differing in detail to a considerable extent can produce similar metallurgical results. It must be concluded that having determined the correct reagent levels, establishing the correct operating conditions are at least as important as machine design. Since about 1960, after 30 years of fairly stable circumstances, manufacturers have been developing new types of machines whose major feature is emphasis on pulp flow characteristics by virtue of new im-peller-stator designs. As far as can be ascertained, these new designs necessitate radical departures from accepted impeller speed-air rate values. Performance data are still awaited. Flotation machine development has been empirical, as is selection of operating conditions. The purpose of the work at Columbia University has been to elucidate the fundamentals of the subject so that the purely mechanical aspects of the flotation process can be understood in hydrodynamic terms.1-6 Hopefully, this might lead to intelligent selection of a particular machine and its operating conditions for a specific ore based on a minimum of testing, or even to new types of flotation machines. The present investigation is the most comprehensive to date.7,8 Earlier work, which was largely exploratory, has been repeated and extended and employes the most accurate measuring techniques available. Additionally, sufficient hydrodynamic data were obtained under flotation conditions to delineate the relevant operating ranges. Attention has been given to scaling in that several geometrically scaled tanks and impellers have been constructed and tested; it has been pointed out elsewhere that undistorted geometrical scaling rarely pertains in flotation machine design.5 This paper is divided into sections dealing with relevant combinations of the three phases: liquid, air and solid. Summaries of the literature have been given in previous publications2-4 and will not be repeated here. Recently, several reviews of mixing have appeared, which can be usefully referenced.9-11 It is of interest to note that flotation is not included

Jan 1, 1970

By Ralph C. Holmer

IN the field of mineral exploration, 1956 can be looked upon as the International Geochemical Year. This is not because of unusual developments in geochemical prospecting but rather because of the world-wide effort in geochemistry and the realization that geochemistry is now an established exploration method. Use of mining geophysics has continued to increase. Those extensively employing exploration techniques indicate that developments of the past few years have permitted better programming of methods, from reconnaissance to location of drill- holes. There is greater diversification of methods- reliance is not placed on results of one. However, it is realized that often it is more economical to drill an anomaly than to conduct additional expensive geophysical surveys

Jan 2, 1957

By E. L. Jr. Spain

THE deposits described in this paper occur over much of Wayne County and in the southeast portion of Hardin County, Tennessee, and in the northeast and northwest portions of Mississippi and Alabama respec-tively. The presence of tripoli in this region has been known for some time and descriptions of various occurrences in Tennessee have been made by Jewell1 and Miser2, while Hilgard3, Lowe4 and Logan5 have treated the deposits that occur in the adjacent portions of Alabama and Mississippi, but there has not been a general survey of the entire field summarizing completely the geology of the deposits with respect to their origin and stratigraphic relationships. During 1934, while engaged in surveys of mineral resources through this region for the Tennessee Valley Authority, the writer collected data with this in mind, and has assembled them in this report. He is indebted to H. S. Rankin and N. A. Rose, of the Tennessee Valley Authority Geology Division, for field assistance.

Jan 1, 1936

By Earl Bardwell

(Butte Meeting, August, 1913.) THE structural relations existing between cuprous oxide and copper were first systematically studied by Heyn1, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming .;from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study off the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing, this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in, this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity.

Jan 7, 1913

Nov. 4, 1952, AIME, Morenci Sub-section, Longfellow Inn, Morenci, Ariz. Nov. 5, AIME, Chicago Section, Chicago Bar Assn., Chicago. Nov. 8-8, New Mexico Mining Assn. and International Mining Days, joint convention, Alvarado Hotel, El Paso. Nov. 7, AIME, Pittsburgh Section, National Open Hearth Steel Committee, off-the-record meeting, Hotel William Penn, Pittsburgh. Nov. 7-8, Birmingham Technical Meeting of Southeast Section, AIME, Birmingham. Nov. 10-11, Eighth Annual Meeting of The Magnesium Assn., Hotel Biltmore, New York City. Nov. 12, AIME. Connecticut Section, Hartford, Conn. Nov. 18, AIME, Buffalo Section, National Open Hearth Steel Committee, Hotel Statler. Buffalo. Nov. 19, AIME, Connecticut Section, Hartford, Conn. Nov. 19, American Mining Congress Coal Div. Conference, Wm. Penn Hotel, Pittsburgh.

Jan 1, 1952

While coal was mined in New Mexico in 1860, production was on a small scale during the period considered here, and Table 77 contains all the data found. [ ]

Jan 1, 1942

By E. S. Machlin

The possibility that formation of voids under creep-rupture conditions may take place by the condensation of vacancies has been investigated theoretically. It has been concluded that nucleation of voids under creep-rupture conditions by vacancy condensation is highly improbable. However, growth of pre-existant voids by vacancy condensation is probable. A number of predictions made in this theory have been verified by the data. It has been predicted and checked that the product of rupture life and steady-state creep rate for preannealed metals and single phase alloys is an approximately invariant quantity, independent of stress, temperature, and atomic number for a given type structure. The direction of the effect of cold work on this product has been predicted and found in agreement with experiment. A number of experiments to evaluate the vacancy condensation mechanism further are described. SEVERAL papers have appeared recently which speculate on the origin of voids formed at grain boundaries under stress.' ' The object of this paper is to examine quantitatively the proposition that the voids produced in a creep test are a result of vacancy condensation. A result of this paper is a theory of creep-rupture. Void Nucleation Application of standard nucleation theory" to the problem of void nucleation leads to the following conclusions: 1—Homogeneous nucleation of voids requires a supersaturation ratio (concentration of vacancies in supersaturated to that in saturated solution) of 400 for a reasonable surface energy of 1000 erg per cm-and 1.4 for the improbably low surface energy of 10 erg per cm. 2—Heterogeneous nucleation of voids at plane interfaces between two phases requires a supersaturation ratio of 2.5 for a typical contact angle of 145 3-—Void nucleation about a solid particle may be accomplished at a supersaturation ratio of 1.17 for a typical value of work of adhesion? of 60 erg per The work of adhesion is the surface work 10 replace two solid-vauor surfaces by a solid-solid interface. enr ' between an oxide and a metal in the presence of a surface active element such as sulphur. Estimates of the supersaturation ratio at which voids are produced in diffusion experiments yield a maximum of 1.01. Inasmuch as the foregoing mechanisms of void nucleation probably will not operate at this level—too low a surface energy is required—the investigatol. is led to the conclusion that voids must already exist. That is, nucleation of voids probably does not occur. Rather, existing submicroscopic voids grow out to visible size. Already existing voids might be produced during solidification or working. Supercritical sized parlicles which contain cracks may act as heterogeneous void nuclei. Gas pockets may act as void nuclei. Experiments are desired to determine the nature of the heterogeneous void nuclei which grow out to voids in both diffusion and creep experiments. Void Growth Void growth might occur in at least two possible ways, depending upon whether the already existing void nuclei are at grain boundaries or within the grains. In the case of a spherical void far from a crystal boundary, vacancies are generated during creep as a consequence of the migration of suitable dislocation jogs' and are also annihilated at sinks. Under these conditions, a steady-state concentration of vacancies is built up in the crystal, defined by the condition that for any differential volume the rate of generation of vacancies in that volume equals the rate of annihilation of those vacancies." This equality would lead to the development of a gradient of vacancy concentration radially outward from the void surface up to a radius where the vacancy lifetime becomes equal for all directions of vacancy migration. The distance over which this vacancy concentration gradient extends equals about 2vD,T* where D, is the vacancy diffusivity and T:' the vacancy lifetime in a crystal outside the gradient in a zone of constant vacancy concentration. The vacancies generated in the region over which the gradient exists will annihilate more often at the void than elsewhere. Approximately a little over one-half the vacancies generated in the gradient zone will annihilate at the void. Hence, the growth rate of the void is given by on where R is the radius of void in centimeters, is the atomic volume, and R is the rate of generation of vacancies, number per centimeter" per second. R D and T* may be estimated in terms of other physical parameters." In particular, R = n.j e/b [3] where n is the average number of vacancy produc-

Jan 1, 1957

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967