Search Documents

By Michael Perch

The fact that coal is a complex organic material and heterogeneous in composition has made its study extremely difficult, particularly in regard to obtaining a fundamental concept of the processes involved in the formation of coke. It has been stated recently that coals are natural polymers and that in a complex reaction such as occurs during carbonization the differences between coals are quantitative and not qualitative. Such being the case, it would be expected, therefore, that a series of coals subjected to exactly the same conditions of coking would produce results that should be related quantitatively to the chemical analyses of the individual coals. In the past, however, this fact was not generally recognized and consequently many empirical test methods were devised for testing coals. The interpretation of the results obtained depended upon comparing a set of data with other data on coals of known characteristics. The testing procedure had to be con- ducted in precisely the same manner each time and not the least requirement in making the interpretation was experience. The test methods varied from those utilizing a gram of coal to the plant-scale tests in which one or more ovens were charged with the test coal. The aim had been principally to find some simple, inexpensive means by which the coke-making and other properties of coal could be predicted. It is not necessary to emphasize the importance of these endeavors, for anyone acquainted with the problems involved in the selection of coals for making coke is well aware of the time and expense involved in making a series of definitive tests.

Jan 1, 1949

By W. O. Crosby

WASHINGTON CAMP, in Santa Cruz county, Arizona, is a small and little known mining district situated on the lower, eastern slope of the Patagonia mountains, about 20 miles east of Nogales and a like distance south of Patagonia Station on the Sonora railroad, which connects it Benson, 83 miles from Nogales, with the main line of the Southern Pacific. This district is also about 4 miles north of the international boundary, 35 miles west of Bisbee and 40 miles north of Cananea, in Sonora. The topography of the district, which lies at a general elevation of 5,500 ft. above the sea, is only very moderately rugged, and presents no obstacles to mining operations. Although some of the claims of the camp, including the Pride of the West, Belmont and Holland, were extensively worked for silver 25 years ago, they passed, at moderate depths, as in so many other districts, out of the argentiferous lead carbonate and sulphide into zinc, copper and iron sulphides; and for two decades the camp was abandoned and almost forgotten. In recent years, however, its apparent possi¬bilities as a copper producer have led to a revival of mining activity; but not, as yet, with conspicuous success. Although economically relatively unimportant, the deposits of Washington Camp are, mineralogically and structurally, nevertheless, typical examples of ore-bodies developed in connection with the garnet ledge now recognized as a normal feature of granite-limestone contacts; and, in the opinion of the writer, this is an instance where a minor example is yet essentially normal and capable of throwing important light upon the origin and genetic relations of the type.

Nov 1, 1905

By Howard S. Bryant

FROM the viewpoint of the oil producer, the oil refiner, the oil marketer, and the investor, in oil securities, a brief picture of the crude oil supply and demand in the present critical season of the year will be timely and interesting. Although crude oil production has been in a comparatively poor statistical position this year, increased sales and sustained refinery and crude oil prices have allowed increased profits for many oil companies. The large amount of crude oil going into storage during the present period of peak consumption, just previous to the major yearly fall decline in consumption, has caused oil producers to make plans to leave the oil in the ground for the present in several of the areas of large flush production. The present moment is looked on as the turning point in the current year.

Jan 1, 1929

By Francis Lucas

ANY metal which contains even a small percentage of aluminum possesses certain peculiarities of appearance and properties which are exhibited both when the metal is melted and after it solidifies. Pure aluminum, or an alloy containing a small proportion of aluminum, can be melted without flux-except for a layer of charcoal-because a film of aluminum oxide and metal forms at the surface of melted aluminum. Although very thin, this film is air-proof, and it prevents the metal underneath from oxidizing. This oxidized film does not move easily on account of its toughness and high surface tension. One very important point in connection with this process of still casting has not been strongly enough stressed, namely, that the same kind of surface film with the same peculiarities forms over the surface of all melted alloys that contain even a small proportion of aluminum. Experienced foundrymen know how desirable it is to cast aluminum under its "skin" or-under the surface of the film which tends to remain still. In the case of red copper, when in fusion, the surface shows pure copper only. This is due to the fact that liquid copper constantly absorbs the copper oxide which forms on the surface. By closely examining melting copper the oxide can be seen dissolving in the bath, and going into solution just as pulverized sugar dissolves in water. When copper is cast in the open, either in wire bars or cakes, the surface of metal exposed to the air is covered by a film of black, oxide that cannot be absorbed by the metal.

Jan 1, 1927

By H. M. Howe

§ 24. Introduction.—This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae3, the upper limit of the transformation range when in equilibrium, as distinguished from Ac3, the temperature at which the end of the transformation is noted in heating up, and from Ar3, that at which its beginning is noted in cooling down. The former is in fact carried above Ae3 and the latter below Ae3 by lag. I touch incidentally on the influence of manganese on Ae3 (§ 29, p. 614). The sections, tables, and illustrations are numbered consecutively with those in the accompanying papers by Howe and Levy on Determination of the Position of Ae3 in Carbon-Iron Alloys, and by Burgess, Crowe, and Rawdon on Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels, to which the present paper forms a sequel. § 25. The contradictoriness of our present evidence is shown by grouping it together in Fig. 14. For instance, both Goerens and Meyer (Series 2) and Meuthen (Series 12) used practically stationary temperature, and thus reduced the influence of lag very greatly; yet Ae3 for 0.32 carbon steel according to the former investigators is 894", but according to Meuthen it is at or below 770°, a discrepancy of 124" or more. In view of our ability to measure these high temperatures within a few degrees, the existence of such a discrepancy is as unwelcome as it seems needless. I attack the thankless task of bringing some order out of this chaos. In Part 11. (§§ 29 to 39) I consider the chief causes of error. In Part III. (§§ 40 to 48) I apply certain corrections to some of the existing data, review those data, weight them, and calculate a prob-

Jan 1, 1914

By E. W. Parker

THE anthracite region, from which there is produced annually about 80,000,000 tons, or approximately 15 per cent. of the total coal supply of the United States, has a combined area of a little less than 500 sq. mi. The total area occupied by the bituminous fields (including the sub-bituminous and lignite fields) is in the neighborhood of 400,000 sq. mi., so that 15 per cent. of the total output comes from this small area of only a little more than 0.1 per cent. of the coal-producing territory. of the United States. The productive anthracite area is divided into a series of basins or troughs, roughly parallel, extending. in a northeast-southwest direction through the. Counties

Jan 1, 1921

Jan 1, 1908

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000' and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,' and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"'" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,'' and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By L. VOGELSTEIN

OUTSTANDING among the year's events in copper has been the reimposition of an import duty of 4r. per pound in this country which became effective June 21. In consequence of this action by Congress, the Ottawa Empire conference recommended a duty of 2d. per pound equivalent at normal rate of exchange to our 4c. duty, on all copper originating outside of the Empire. Lip to the middle of this year only Russia and Japan had a closed market; the import duty on copper in Russia is 30 per cent ad valoremm and in Japan about 2c. Russia's consumption has always been in excess of production and she has imported from 2(1,000 to 40,000 ton, of copper per annum. Japan, with a production of 6,000 to 7,000 tons per month, has absorbed, in normal times, its production, but during recent: sears has exported varyiug quantities in 1929. 2,200 ton-: in 1930, 2,700 tons, and in 1931. 3,600 ton-. Aside from the-e two countries, the international market has heretofore been free. It and when the British Empire duty become, effective the world's markets will be divided into four unit: 1. Russia and Japan, 2. United States. 3. British Empire. 4. Rest of the world. The world's production at present is rennin it the rate of 930.000 tons per annum. This year's production will be over 1,000,000 tons because the several curtailment did not become effective until the second quarter. consumption will be slightly in excess. Deducting from 30,000 tons Russia's and Japan's production of 121.000 tons, 806,000 tons is left divided a, follows:

Jan 1, 1932

By E. W. Pehrson, J. W. Furness

THE five charts presented here- with are part of an original group prepared by the U. S. Bureau of Mines showing the international trade in the principal metals and metallic ores. Charts 011 anti- mony, chromite, copper, lead, manganese, mercury, nickel, tin, tungsten, and zinc were published in the February, 1936, issue of the Engineering and Mining Journal. Those shown here include bauxite, aluminum, iron ore, pig iron, and the platinum-group metals.

Jan 1, 1936

By J. J. Rutledge

I. DESCRIPTION OF THE CLINTON ORES AND ASSOCIATED POCKS. THE Clinton rocks in Stone Valley comprise (1) thick layers of deep-red shale, (2) layers of reddish-gray shale interspersed with beds of sandstone and thin beds of extremely fossiliferous limestone, and (3) yellowish-gray shales alternating with thin layers of olive-colored shales. These layers of shale are all very thin and are at no point massive.1 A bed of gray-white sandstone varying in thickness from 12 to 30 ft. occurs in the tipper portions of the Clinton shales. This is called the ore sandstone, a name given to it by Rogers and adopted also by the Second Pennsylvania Geological Survey. It is the surest guide to the presence of the iron-ore bed, which lies below its lower edges at distances varying from 10 to 20 ft. This ore sandstone, in the valley, lies generally at very low inclinations, but often is locally subjected to considerable changes in dip. At its outcrop this ore sandstone weathers very easily and yields a rather sparse crop of stone, Composed of dirty, iron-stained boulders. Upon the roads these boulders are quite well rounded, and bear fragments of crinoid stems and other fossil forms. The ore sandstone exhibits at many points evidences of former movements in this very great thickness of the shales, and as it is the only stratum in this series competent to transmit and record stresses due to structural movements, its evidence is of considerable importance in determining the occurrence of movements in times past.

Nov 1, 1908

By Douglas Bunting

(Wilkes-Barre Meeting, June, 1911.) WITH the gradual exhaustion of the upper veins in the anthracite coal-fields, the problem of mining at greater depths acquires increasing importance and demands the consideration of a number of important factors, one of which is the greater earth-pressure and the consequent necessity of stronger support o for the roof. Under the pillar-and-chamber system, almost exclusively followed in the Northern anthracite-field, the highest economy in mining is generally secured by leaving, on first mining, pillars only sufficient to support safely the overlying strata. As to the necessary size of such pillars, the opinions of mining experts are widely divergent. In establishing the width of chambers and pillars, the thickness of vein and its depth below the surface have received little consideration. For. instance, it has been quite usual to work both overlying and underlying veins with the same width of chambers and pillars, when the lower vein was two and one-half times as thick, and twice as fits below the surface, as the upper. In view of the generally-accepted theory that the crushing-strength of coal-pillars of the same base-area becomes less with increased height, it is probable, in this instance at least, that the most economical mining has not been secured. This question of adequate pillar-support is economically less important down to about 800 ft. than at greater depths; and it is with reference to mining at these greater depths that the study of the subject here presented has been prompted. The necessity of leaving larger pillars, involving greater mining-costs per ton and also smaller yields per acre, is one of the troubles of deep working. To mine without leaving adequate pillar-supports will result, sooner or later, in a squeeze. Limited areas, it is true, have been mined at certain widths of

Sep 1, 1911

By D. R. Walker, M. C. Shaw

Dimitri Kececioglu (Allis-Chalmers Manufacturing Co., Milwaukee)—The idea of applying metal cutting theory to comminution and vice versa is very impressive. Among others, the demarcation of wheel-grinding data into two regions, namely Kick's and Rittinger's, draws attention here. A study of Figs. 6 to 9 shows the following: In Fig. 6, 1 point out of 8; in Fig. 7, 4 points out of 26; in Fig. 8 only 1 point out of 13; and in Fig. 9 practically none out of 13 points fall out of curve No. 2. Also when grinding particles smaller than 5x10." in. it is difficult to measure very accurately the grinding forces, chip geometry, and particle size. In view of the above it would be difficult to make a positive and distinct demarcation of the Wheel-grinding data into two regions, namely, Kick's and Rittinger's. The idea of using machine grinding to determine the comminution properties of materials is indeed unique. The following cautions come to mind, however, regarding applicability of machine grinding data to comminution: 1—Grinding gives uniform particle size, whereas comminution gives a variety of particle sizes in the same process. The fact that grinding gives uniform particle size is not necessarily an advantage because in comminution the overall energy under actual comminution is desired and comminution invariably results in the production of a variety of particle sizes. 2—In grinding, a small particle is ground off a comparatively large surface. In comminution small bodies are broken down to smaller bodies. This makes it difficult to establish a concept of reduction ratio in machine grinding. 3—The mechanics of machine grinding involve direct shearing action under very high strain and comparatively high compression at the shear zone, whereas: comminution involves direct dynamic compression and surface friction with comparatively little strain and shear. Consequently the mechanics of machine grinding appear to be different from those involved in comminution. Hence one might arrive at erroneous con- clusions when comminution characteristics are eval-uated from machine grinding results. It is noticed also that functions other 'than Eq. 16 which do not involve the concept of direct proportionality of useful energy input to new surface area created (Eq. 2 and particularly Eq. 12) may be derived to fit the, data of curve No. 2. One such relationship may be u = ct-", where c is a positive constant and n is a positive constant less than unity. This, of course, is made possible because data of a very small range. of particle size are being fitted by the curves of No. 2 and the hereby suggested relationship. A sound comminution theory should be applicable to a relatively large range of particle size. George B. Clark (Department of Mining Engineering, University of Illinois)—While the experimental work of Walker and Shawin this article is of intrinsic value in revealing certain fundamental aspects of machine grinding, milling, and related processes and in adding to the store of information concerning the comminution of solid materials by this particular process, it appears doubtful that the results of their research can be employed to verify either Kick's or Rittinger's theories. Both these laws were originally developed and proposed on the basis of very simple, idealized hypotheses. The creation of parallel idealized physical laboratory conditions which would be required for either their proof or disproof appear to be well beyond the scope of human ingenuity, at least at present. One great weakness of the imputed verification is that the spread of the points plotted on the graphs is not sufficient to permit accurate 'curve fitting. The range of particle sizes included in the belt and wheel grinding is not extensive enough to show any general trends, particularly for the horizontal portion of the curves, said to represent Kick's laws. That the milling; grinding, and turning data obtained by Walker and Shaw for both metals and minerals happen to comply with. certain interpretations of these two theories under certain specialized conditions

Jan 1, 1955

By C. Laird, C. E. Feltner

An investigation into the effect of a material's slip character on its high strain fatigue properties has been carried out using copper and Cu-7.5 wt pct A1 as representative wavy and planar slip mode materials, respectively. In copper, the constant term and exponent in the Coffin-Manson equation, ?EpNf1/2 = const, are unaffected by the temperature of testing or the history of the metal. On the other hand, in Cu-7.5 wl pcl Al, while the exponent is invariant, the constant is increased with respect to copper and increased further with decrease in temperature. The life in Cu-7.5 wt pct A1 is double that of copper at room temperature and about four times at 78°K. Fractoflaphic studies indicate that these diffevences in life are associated with the early stages of cracking. In copper, severe surface rumpling provides crack nuclei at pain boundaries independent of' testing temperature or the history of the metal. In Cu-7.5 wt pct Al, the planar slip mode of deformation prevents grain boundary folding; crack nucleation is therefore mainly transgranular and the increase in life with respect to copper is associated with a prolonged linking-up stage of such transgranulay cracks. At the lower temperature the increased difficulty of cross slip inhibits multiplication of trans-granular cracks and retards the linking-up process, giving a further enhaancement in life. It is expected that such behavior will be found general in materials of wavy and planar slip mode, respectively. STAGE II crack propagation in high strain fatigue takes place by a repetitive process of crack tip blunting in the tension part of a fatigue cycle followed by resharpening of the crack in the compression part.1-3 This mechanism has come to be called the "plastic relaxation process".3 At very high strains (lives to failure less than 103 cycles), most of the life of a specimen is spent in crack propagation by the plastic relaxation process.4,5 Since the differences in the cyclic strain hardening behavior of metals and alloys are comparatively small in this strain range,6,7 the amount of blunting at a crack tip depends primarily on the applied strain amplitude. The rate of crack propagation in this life range is therefore nearly constant with respect to material and temperature of testing. In the longer life portion of the high strain fatigue range (l03 to 103 cycles to failure), a considerable fraction of the lives is spent in crack initiation and Stage I growth. Grain boundaries have frequently4,5,8 been found to be the sites for this growth which is also associated with a surface folding process.4'5 Such folding behavior may also be general in any material having a grain structure and capable of plastic deformation. It has therefore been suggested475 that the universality of the Coff in-Manson law,9'10 constant,* where ?Ep is the plastic strain range and Nf the number of cycles to failure, is reflected in the approximate invariance of both the crack initiation and propagation behavior. It happens that, in most investigations of the phenomena associated with failure,4,5,8 materials with a wavy slip mode have been used as vehicles for the studies, or else "normally" planar slip mode materials have been tested under conditions giving rise to wavy glide deformation, e.g., stainless steels cycled at high temperature.'' The purpose of the present investigation was to determine whether or not different cracking phenomena would occur when the slip mode of a material is planar and if the associated life to failure would be different than that of a wavy slip

Jan 1, 1968

By Wayne E. Tuomi

The mining industry is faced with a pressing problem; that is, to develop more efficient methods of extraction, handling and upgrading-techniques that will do the job faster and better than ever before. New techniques require new machines, or applications of new and improved materials that can be used to modify and improve existing machine and equipment designs. The traditional approach has been to increase productivity by increasing equipment size. Prognostication indicates that the trend toward larger equipment sizes and capacities will continue as one answer to the challenge imposed by future increases in mineral demands. But what is the limit on the continued growth of equipment size? Until about 1930, there was a very definite limit-a limit imposed by the strength of the steels and the power plants then available. The equipment engineer had come to an impasse: even though it was easily possible, for instance, to triple the size of a bucket, it had become impractical to correspondingly enlarge the boom, the counterweight, and the power plant.

Jan 3, 1967

By Alan F. Stewart, Douglas R. Piteau, Dennis C. Martin

Three examples of open pits where toppling failure controls the stability and design of the slopes are described. Two examples involve the design of overall slopes in base metal mines. The third example concerns the analysis and design of remedial measures to prevent toppling failure from occurring in a critical slope in a coal mine. The analytical techniques for assessing toppling failure on a rational basis are discussed for the three examples. This includes an assessment of the important parameters which govern the stability for the toppling failure mode. The geological setting and input data for each example are described, as are the important external or limiting factors pertinent to the sites in question. A statistical cumulative technique was used to assess one of the most important input parameters in the two examples involving overall slope design. Both deep-seated toppling failures, involving the entire slope, and shallow bench failures are considered. Results of the stability analyses and their related engineering significance with regard to slope stability and design are discussed. A sensitivity analysis of various parameters is effectively utilized. Design charts are developed and evaluated accordingly. In the example where toppling failure was unavoidable, the rationale for design of stabilization techniques to prevent toppling is discussed.

Jan 1, 1983

By Francois Clerf

IRON ORE fields are situated in both the East and West of France (see maps). The eastern deposit is by far the most important from a tonnage point of view, not only in France, but in all Europe. The ores of this region are known as minette, and are situated in the Lorraine ore fields and the Briey plateau. The iron ores of the West are those of Normandy, Anjou and Brittany. Before the war, a large number of important German companies had acquired considerable interests in these western fields and a heavy trade with Westphalia had begun. Recently, however, conditions have changed and some of the mines of Brittany and Anjou are now idle. From a geological point of view, in Anjou and Brittany, a series of synclines extends from the northwest to the southeast, containing a number of seams of varying thickness and generally intercalated in Silurian and sometimes in Devonian formations. The ore is generally a hematite or a magnetite. The composition varies from 48 to 52 per cent of iron and from 8 to 12 per cent of silica. Con¬servative estimates indicate a con¬siderable tonnage of workable ores (150,000,000 metric tons).

Jan 1, 1936

By HUBERT O. De

IN December, 1936, several drilling tests were made at the Hubert O. De Beck feldspar mine at Green Mountain, N. C., to determine the most efficient type of hammier-drill bit and drilling method for use at this particular property. This mine is well recognized as having the hardest rock in the Burnsville - Spruce Pine feldspar district and drilling costs always have been high. Local structural deformation has greatly distorted and warped the normal crystalline structure of the feldspar so the rock is much tougher than usual. In studying drilling methods and bit types, available literature was re¬viewed but little specific data could be found on the direct comparison of four-point and six-point drill bits so the following results may be of some interest.

Jan 1, 1937

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By Sir Lowthian Bell

WITH the exception of air and water, it is open to question whether there is any form of matter which the human race could less easily spare than iron. Short of going the length of asserting that, without this metal for an anchor or steel for the compass, the adventurous navigator could never have crossed the wide Atlantic, we may credit the locomotive' and the steamer, and hence iron, for that sequence of events which has peopled North America with the

Jan 1, 1891