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By Louis C. McCabe

The control of dusts and fumes of submicron size is involved in many process industries. This paper presents in tabular form the quantitative data from a number of metallurgical operations and discusses allowable discharge in terms of effluent-weight ratio. Typical installations for recovery of stack effluents are cited. THERE are many sources of smoke, fumes, gases, and dusts that may cause undesirable contamination in an industrial area. Fumes and gases are the result of chemical action or volatilization, while dusts are produced in processes of disintegration and dispersion. Commonly, smokes are suspended particles formed by combustion or destructive distillation. Methods for controlling smoke are generally known, and great improvements have been made in equipment for removing fine dusts and fumes from gases. In most of the industrial centers of the country, the chief duty of the air-pollution abatement agency is the elimination or reduction of emissions resulting from improper combustion. Correct methods of firing, proper fuel selection, and installation of properly designed equipment may accomplish this. It is becoming more widely recognized that much of the contamination of an industrial atmosphere is caused by dusts, fumes, and gases that are not related to the process of combustion. As such emissions are usually a functional part of plant operation, they rarely can be prevented even by better design and careful operation. When dusts, fumes, and gases are an integral part of the operation, mechanical equipment must be designed to remove these emissions. Most of the dusts and fumes that should be controlled are less than 1 micron in size. Control of such small particles is largely a new and untried field in many industrial areas. However, where conditions have been critical, effective control equipment for dusts, fumes, and gases has been in operation for many years. The problem is not one of smoke abatement and requires an entirely different set of standards for effective solution. Identical standards need not be applied to all industrial areas because of differences in meteorology, physiography, plant location, plant density, and nature of stack effluents. In this paper, discussion of control of atmospheric contamination by industrial plants refers specifically to the Los Angeles area, but the method of approach is applicable to any area where similar problems are encountered. Quantities of particulate matter reported in analysis of stack effluents indicate the need for standards of emission. Many types of dusts and fumes that contribute materially to the air-pollution problem are discharged into the atmosphere at a lower rate than 0.40 grain per cu ft at standard conditions. On the other hand, some stacks discharge at a higher

Jan 1, 1951

By R. Adair, W. R. Hudspeth, W. T. McDaniel

D. C. Ralston (U. S. Bureau of Mines, Washington, D. C.)—Flake mica can be beneficiated by a wider variety of methods than almost any known mineral. However, most of these methods are not recorded. It is therefore a pleasure to find a written record of another application of a new method of beneficiation. The fact that the Humphries spiral gives a concentrate containing the mica flake mixed with the slime and small grit has forced a further separation by screening, in which the finest of the flake will pass through. Fine flake has its uses and if mixed with slimes or clay is recoverable reliably only by flotation. This loss must be charged against the spiral. On the other hand, the new muscovite mica paper recently brought out by General Electric Co., can be made only with grit free flake larger than 50 mesh. It is of interest to learn from the authors whether the washing of the flake on a 50 mesh screen can take the grit content below 1 pct, to meet this new demand. Must another degritting process be used on the flake, like electrostatic treatment of the dried material? H. D. Snedden (The Humphreys Investment Co., Denver)—When recovering mica in the spiral, gangue particles coarser than 16 mesh can be rejected more readily when operating at a high pulp density (35 pct solids) or a low volume rate (—15 gpm). A launder screen as used by Lehigh Coal Co. has proved very satisfactory to partially dewater the mica concentrate and to reject any gangue slimes it may contain. Under certain conditions mica cleaning in the spiral can be improved by reagentizing the spiral feed, the object being to insure wetting of the gangue minerals and to agglomerate or prevent wetting of the mica particles. R. B. Adair (authors' reply)—The grit content of the mica recovered on Humphreys Spirals varies with the fineness of the launder screen used to clean the mica product. Normal practice has been the use of 80 mesh screen, which will produce a mica product of acceptable grit content for most purposes. By using a 50 mesh screen, and increasing the screen area per ton of feed, it is felt by the authors that a mica of 99 pct plus purity could be obtained. This statement would hold only in the case of mica feed which was well de-laminated, and free from "clay balls," (semikaclinized feldspar), which tends to follow the mica through the process.

Jan 1, 1952

By L. C. Armstrong

A. E. ROSS*—Mr. Armstrong in his paper stated that they had experienced considerable difficulty in drilling the quartz-feldspar intergrowths. The dia-mor~d loss was excessive and the diamond bits polished quite rapidly. Mr. Davidson, who presented the paper, stated that bortx stones in the range of 20 to 30 per carat had been used in the bits on this job. I would like to suggest the use of bits employing stones in the range of 60 to 100 per carat, an average of possibly 80 per carat. If these stones had been used the bits might have lasted longer and not polished so quickly. As a basis for this suggestion I would like to point out that in northern New York State we had at least two examples where bits employing stones in the range of 80 per carat had solved a difficult problem. Bits set with stones in the range of 20 to 30 per carat had been used previously and had failed. With the finer stones, the cost per foot of drilling decreased material1y. It should also be noted from a technical standpoint that the smaller stones require higher drilling speeds than the larger stones. Greater pressures are not normally necessary, and it is the higher speed which seems to be the major factor of importance. It should also be noted that the finer stones afford a greater number or cutting surfaces for the same carat weight in a bit. Then too, the smaller stones, by virtue of their size, serve as sharper cutting edges than larger stones. There is no doubt that the diamond bit employing smaller stones costs more to set than the bit using larger stones. However, with the technique developed at the shops of Sprague and Henwood, Inc., we feel that the relatively slight additional cost required to set these bits is more than paid for by the resultant lower drilling cost. We feel that the highest quality stone available is the most economical to use when hard fine grained rock is encountered. In summary, I would suggest that it might be possible to solve the problem presented in this paper by using a diamond bit employing stones at least as small as 80 per carat of the highest grade possible and by using the diamond bit at the highest speed available with modern drilling equipment. L. C. ARMSTRONG (author's reply) —It is generally agreed that the use of smaller, high-grade diamonds and of higher drilling speeds, as suggested by Mr. Ross, may be the best approach to the solution of the problem.

Jan 1, 1950

By R. P. Olsen, A. K. Schellinger

Molten silicate salts, the important industrial byproducts termed "slags," are known to be electrolytic conductors at furnace temperatures. This property is due to their partial dissociation into ions with the ion kind and size being closely related to the slag composition. Ionic conductance, in liquids, is a function of the viscosity, which in turn is a function of the temperature. It could be anticipated, therefore, that a semi-log plot of conductivity vs. reciprocal absolute temperature might yield a straight line, in the case of molten silicates and salts. As liquids, the viscosity of these slags should follow the Shepard1 relationship: log viscosity = A/T + B Then, if the resistance of the molten slag is directly proportional to the viscosity: log Rs = A/T + B Resistance measurements of molten halide salts,2 and silicate salts34 by various investigators have, indeed, shown this straight line relationship between resistance and temperature. A further relationship between the conductivity versus the degree of ioni-zation, the size of the ions, and the slag composition is, also, to be expected. Large ions, and fewer ions, would move more slowly in a potential field and could not carry as much current as smaller, more numerous, and mobile, ions. Conductivity, therefore, would be smaller in the presence of such large ions and higher slag viscosities. The conductivity-composition relationship is of considerable interest in the case of the industrial slags produced in iron blast furnaces, and non-ferrous smelting furnaces. These slags usually approximate three component systems with several minor components as impurities. At least one of the major components is commonly purchased for the sole purpose of rendering the slag less viscous at a reasonable furnace temperature. Should the conductivity be related rather directly to the concentration of such a purchased slag component (that is, CaO) instrumental measurement and control at the furnace might be possible. Modern tele-metric control methods in aqueous chemical process industries are often based on the property of conductivity of solutions, and its variation with composition. Investigators3 of the phenomenon of electrical conductivity in molten blast furnace slags have established that these systems show lines of equal conductivity on their ternary diagrams at one temperature level. These isocon-ductivity lines form closed contours on the diagrams, and at times, minimum areas occur at which these contours are essentially closed down to a point. The conductivity reading at such a point, at one temperature , would, of course, locate one on the diagram, and give the slag composition. Research in this field is understandably scanty. The reactive nature of

Jan 1, 1950

By William P. Blake

The occurrence of enormous masses of pure copper has given the mining district of Lake Superior worldwide reputation. The first masses brought from there excited great attention, and directed the notice of the mining world to the few particular mines from which they were taken. It may not now be generally known that nearly all the veins which are worked, and which cut across the trap ridge, contain mass copper, and that large masses are continually being raised from them. The largest continuous mass which has been taken out was probably that from the Minnesota, in 1857, which is variously stated as weighing 420 tons and 470 tons. Its length was about 45 feet, its breadth or height 22 feet, and its greatest thickness 8 feet. All such masses are very irregular and ragged in their form and thickness, thinning out generally from a foot to a few inches, and straggling through the vein until they connect with other large masses. This was the character of a mass found in the Phœnix Mine, one of the oldest on the lake, which mass altogether weighed some 600 tons. But this was really a series of masses more or less connected by strings of metal, yet no one large part of it weighed, singly, over 200 tons. A similar series of masses, weighing about 600 tons, was extracted from the Miunesota. Some of the Phœnix masses were four to five feet thick of solid copper. The Cliff Mine has yielded masses weighing from 100 to 150 tons in one piece. One of 40 tons was taken out this year, besides numerous blocks weighing from 1 to 8 tons. This mine and the Central are now yielding mass copper in abundance. It is, bf course, impossible to pick, or drill, or to break out such huge masses of solid metal when they are found, by drifting upon the course of the vein. The method of extraction is as follows: The miner picks out or excavates a narrow passage or chamber upon one side of the mass, laying it bare as far as possible over its whole surface. It is usually firmly held by its close union with the veinstuff, or by its irregular projections above, below, and at the end. If it cannot then be dislodged by levers, the excavation of a chamber is commenced behind the mass, and this excavation is made large enough to receive from 5 to 20 or more kegs of powder. In one

Human engineering was the keynote of the thirty-ninth annual meeting of the American Society of Mechanical Engineers, which was held in New York, December 3-6. This note was sounded by President Charles T. Main in his address at the opening session and was carried through by all the speakers. In his survey of the year's work, he said that more than 6000 names of engineers were furnished the Government for filling a wide variety of positions. In addition to the 1400 members in service, two members of the council of the society are in uniform in France and one, as a distinct war service, is in charge of one of the largest shipyards. After giving other ways in which the Society has helped the Government, President Main called attention to the necessity for thoroughgoing efforts to increase production and the settlement of questions involving industrial relationships. At the following meeting, President Adams of the American Institute of Electrical Engineers called attention to the necessity of meeting labor in a progressive way, facing labor questions fairly and squarely, as the real interests of labor cannot be separated from those of the engineer. Charles E. Knoeppel, discussing "Industrial Organization as It Affects Executives and Workers," said the problem of the cost of living might be settled in two ways: 1, there must be more producers, and 2, there must be a greater amount supplied by those now producing. The first solution is practicable, he said, if labor is allowed shorter hours, better conditions, and a remuneration that will attract workers. The second can be employed by eliminating waste, standardizing conditions, setting fair tasks, and allowing men to earn an amount that will compensate them for' their skill and cooperation. Dudley R. Kennedy of Philadelphia, employment manager of the American International Shipbuilding Corporation, said the human-engineering phase of the country's industrial development had generally been overlooked. "We hardly yet know what competition means; we will learn it within a few years. Permit me to prophesy that the executive of the next decade will be the man who best knows men. He will be an originator, a handler of men as individuals, a handler of men in the mass, a leader not a driver, a very human man. The science of human engineering is here to stay. The study of human characteristics is the most enduring, as well as the most fascinating in the world, and still the most complex."

Jan 1, 1919

By Geoffrey Gilbert

THE Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since I930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. HISTORY The occurrence of rock phosphate in Montana has been known. since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Consolidated's phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 ¾ miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. GEOLOGY The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. Of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1945

By Woolsey Johnson

THE object of this paper is to, describe the several necessary characteristics of the zinc-retorting charge and to show how by certain improved methods; the large excess of coal, over that theoretically required, can be reduced, thereby effecting an increase in the smelting capacity of a retort plant as well as other economies. In the Southwestern zinc works a charge of roasted zinc ore with a side mixture of carbonates and silicates, analyzing on the average 50 per cent. Zn, is mixed with 55 or more per cent. of its weight of a mixture of coal and coke analyzing 60 to 70 per cent. fixed carbon. . The ore is of varying fineness and the coal and coke are usually crushed in a semi-moist condition through a 3/8 -in. screen. With ores of a slaggy nature, this coal proportion is increased, sometimes to as much as 100 per cent. of, the weight of the ore. With carbonate ores, or where anthracite screenings with higher carbon content are cheap enough, the percentage of reducing agent is cut to 45 per cent. or even somewhat lower. The average charge per retort for a monthly run of a plant on ore, as distinguished from retorts on blue-powder, ladle-skimmings and other between-products, runs from 60 to 66 lb., with a mean of 63 lb. for the Southwest with standard retorts of 8 ½ -in. inside diameter and 50 in. long inside, using roasted sulphide ores. Conditions will change these figures, but 40 lb. of ore per cubic foot of retort space is, I believe, an average in the better-operated plants. Since the rise in. the price of spelter, the tendency has been to overcharge. To remove the slag that is formed when retorts are overcharged, extra men are put on to "gum-chisel" the retorts to prevent "set" furnaces and "butchered, retorts." Taking the above conditions as premises, we find that from four to six times the amount of coal necessary for the reduction is used, as is evidenced by the fact that the residues analyze as high as 35 per cent, fixed carbon. There are good reasons why this excess of fixed carbon must be used and perhaps these can be best explained by a description of the metallurgical requisites of a zinc charge. We may enumerate these as follows: 1. High reducing power, especially at the end f the shift, to reduce any carbon dioxide to monoxide and bring about a good condensation

Jan 2, 1918

By W. R. Jones

composition, he cannot reasonably asl; the manufacturer to guarantee that this composition shall give certain physical results. W. R. Jones, Pittsburgh, Pa. : The question that naturally occlun to me is this: Has Dr. Dudley in his inveatigtrtions been aiming to prove a theory, or has he been guided by an earnest desire to discover what are the proper elements in the composition of a good-wearing steel rail ? Unfortunately, for correct chemical information, he has omitted in his analgw two very importnat elements,—sulpbur and copper. Now, before we will even begin to admit the correctnets of Dr. Dudley's conclusions and the formula he prescribes, we will at the start question the propriety of any chenlist or scientist prescribing a formula for making steel when he has iguared such important ele ments as sulphur aud copper. I, for one, will not accept any such formula. Are we sure, or is Dr. Daclley sure, that the chemical analyseq embodied in his paper are correct? This may seem a presumptuous queetion, yet, with my experience with chenlists, I naturally doubt the correctness of the analyse8, and, before I will accept them as correct, I will ask that comparative tests of phosphorous and man ganese be made by the Pennsylvania Railroad chemists and the chemists of the leading steel-works in the country. Let us first verify the correctness of the analyses before we consider the con clusions. I can enumerate a great number of instances in which chemists have differed very widely in their determinations of phos phorus and manganese. A prominent iron fitam made a contract with the Edgar Thomson Steel Company to deliver pig metal guar anteed to be between 0.07 and 0.08 phosphorus; an analysis by our chemist resulted in phosphorus 0.148 and 0.152,—a rather startling difference! Again, a sample bar of steel, in which our chemist reported phosphorus 0.11, was tested by a chemist of au other Bessemer works, ana his determinations were phosphorus between 0.07 and 0.08: A leading engineering establishmeut of Pittsbdrgh bought iron claimed by a chemical analysis to contain 0.08 phosphorus; our Mr. Ford found phosphorus 0.145. A chem ist connected with an open-hearth works reported manganese in a piece of steel, 1.14; in a second determination from the same piece of steel, by the same chemist, manganese was reported 0.43. The chemist was kept in ignorauce of the fact that both samples were from the saw piece of steel. Two dctermiuations for manganese

Jan 1, 1881

By O. U. Bradley

The extent of losses, due to evaporation, sediment, and water, in crude oil stored in steel tanks, is a very interesting question, and particularly so at this time, when every reasonable measure should be employed to eliminate all possible losses of this important natural product. Available information on this subject is incomplete; e.g., during the development of the Cushing Field, considerable surplus oil was stored in steel tanks, but from time to time, owing to changes in weather, some losses by evaporation and short storage room on the leases, these tanks were topped out, thus rendering inaccurate any system designed to determine the average rate of evaporation or other losses of the oil over a given period. Furthermore, the losses, as shown by the records at the time, as a result of hasty gages, failed to take into account the temperature and gravity of the oil. Losses may be classified roughly as occurring from evaporation, presence of sediment and water, and leakage. The coefficient of expansion and contraction of crude oil, in relation to temperature conditions, is of material importance; also, the rate of evaporation is dependent upon the gravity of the oil, as the escape of the lighter hydrocarbons in fresh Cushing oil, of from 40 to 42 gravity, on a warm day is considerable, and from available records of temporary storage, it is safe to assume that a loss of 1 to 11/2 per cent. in volume will easily occur in light crude oil of Cushing grade over a period of 6 months, including the summer season. The presence of sediment, water, and other impurities, in the oil will also cause more or less deterioration in quality, particularly when the fresh production is run direct from the gage tanks, or from the wells on the lease to steel storage, as is often the case when an oil field is being rapidly developed. The bad oil will settle to the bottom of the tanks and may be determined by thiefing and running a centrifuge test on the sample. The amount of water in the oil depends entirely on the conditions under which it is produced. Sometimes in large producing wells, with heavy gas pressure, some water may come in with the oil, particularly if the well has been drilled to the top of a water sand. Under these conditions, cut oil is often produced, which, if not settled out, is carried over into the steel tanks. The losses by leakage in steel tanks are difficult to determine, for

Jan 1, 1920

By L. G. Truby

DISCUSSION By Rhrt G. Nisle, Phillips Petroleum Co., Barthesville, Okla. The subject paper presents the results of a reservoir behavior analyzer study of the pressure-production performance of five Ellenburger pools in West Texas. These five pools are Wheeler, TXL, Andector, Embar, and Martin. This laboratory has also made reservoir behavior analyzer studies in this area and arrived at substantially the same conclusions. Although the principal results of the studies made in this laboratory are confirmed by the results in the subject paper, there are certain points of difference. The points of difference are (1) the subject paper includes the Martin pool in the common aquifer, whereas our studies indicate that it is not, and (2) the subject paper concludes that the effective aquifer is considerably smaller than that derived from studies made in this laboratory. In terms of reservoir analyzer data, our rejection of Martin is based on the inability to obtain a satisfactory match of the pressure curve when Martin is considered as lying within the common aquifer. A satisfactory match was possible, however, when Martin was run as an isolated pool. This indicates that the pressure disturbance resulting from production at Martin had not reached Embar, Andector, TXL, or Wheeler at the time of our study. A similar situation exists relative to Dollarhide. In tern of geological data, our rejection of Martin is based on the presence of a faulted zone between Martin and Embar. This condition is indicated in Fig. 4 and again in Fig. 10 of the subject report. If a permeable connection between Martin and the other fields does exist, it is probably by way of a detour around this fault. The second point of difference between the two studies is illustrated by a comparison of Fig. 4 of the subject paper with Eg. A. Fig. A is obtained from an internal report on one of the studies made by this laboratory. It will be noted that the area indicated in Fig. 4 is roughly that marked "Pool Unit" in Fig. A. The additional portion of the aquifer shown in Fig. A was simulated on the reservoir analyzer by means of the water drive network. A satisfactory pressure match could not be obtained without this additional network. The differences involved here stem from a more fundamental consideration concerning reservoir analyzer operating techniques. The true source of these differences in reported results cannot at this time be determined because of the incompleteness of the subject paper. It is not stated, for instance, whether the pressure match was induced by altering the field resistance or the field capacitance, or both. Changing analyzer

Jan 1, 1953

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

Jan 1, 1944

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

Jan 1, 1944

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200 °C, a wide range of conveyors is available. Special constructions of rubber conveyor belts, steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400 2F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F. The arbitrary selection of 400 °F as a dividing point undoubtedly can be challenged, as special conveyor belting constructions are available which are suitable for temperatures in excess of 400°F. However, when the relatively short life of such belts and the cost of their replacement, with the attendant down time, are balanced against the reliability and long service life of the properly designed steel constructed units to be discussed, there is little question in any operator's mind that the special belts are more expensive to use. Because the conveyors under study are for the handling of bulk materials, inevitably including a high proportion of fines, obviously wire mesh belts cannot be included for consideration. Even though this type of conveyor is widely used at high temperatures, i.e., for carrying glassware through a lehr, it is unsuited for the conveying of bulk materials, and therefore will be excluded from further discussion in this paper. Preliminary to the study of the conveyor itself is the determination as to whether the material is to be cooled while it is being handled, or whether the processing requires retention of all heat and the maintenance of a given temperature range. In the majority of cases cooling is incidental to or part of the handling process, when the handling, for example, follows completion of sintering, roasting, calcining, refining, or some other process. To meet such operating conditions successfully, the conveying medium used must have: 1—a construction capable of withstanding maximum initial temperatures of the material being handled. 2—a construction providing efficient heat transfer for cooling. 3—a construction providing dependable operation and long life with minimum service requirements, and 4—a construction providing controlled and efficient conveying. Under the usual conditions of cooling during the handling, the construction selected to withstand the initial maximum temperatures does not necessarily involve using alloys, as excellent results can be achieved with normal carbon steels and cast irons, when they are properly applied and proportioned. The earliest and simplest type of conveyor for handling very hot materials is the cast steel drag chain conveyor, still widely used for handling hot cement clinker, as illustrated by Figs. I and 2. Because of the rugged and generous proportions of the chain link design, low carbon steels are entirely suitable for the links. The pins, however, must be alloy steel. The simple, rugged construction of this type of conveyor makes it readily capable of withstanding high initial temperatures, even though the chain is operating buried in the material. The drag-chain type of conveyor has advantages and limitations. Although the efficiency of the heat transfer is relatively poor, the life of the conveyor is reasonably long, and because of its crude simplicity it does not require much servicing. However, as a conveyor, it is limited in capacity, and largely limited to horizontal runs. Furthermore, because of the crude design, heavy weight, and the chain operating at the temperature of the material, greatly reducing permissible operating chain pulls, this type of conveyor is limited to relatively short centers. Another type of conveyor that has been used for very hot materials is the cast pan conveyor. Because of its very generous proportions the cast pan, which is made of either cast iron or malleable iron, can withstand initial maximum temperatures. It also provides efficient heat transfer for cooling. Further, it is on efficient conveyor construction, which can be used for inclines. Because the chain employs rolling friction instead of sliding friction, and is not in the maximum temperature zone, much longer centers are possible. It is this type of conveyor that is frequently used in the casting of various metal pigs, pig iron, and aluminum; it is obvious, therefore, that very high initial temperatures are being handled. With this kind of conveyor the return run is frequently sprayed with water to accelerate heat transfer. The build-up of residual heat in the very heavy cast pans is thus overcome. The outboard roller steel pan conveyor is an improved pan conveyor' which provides high rates of heat transfer and substitutes formed steel pans for the heavy cast pans. It is a very efficient conveying medium. The details of this particular construction are clearly shown in Fig. 3. An early application of this type of conveyor is shown in Fig. 4. In this case the conveyor units are handling roasted phosphate rock at average temperatures of 1000" to 1500°F, and frequent maximum temperatures as high as 1900°F. Several widths are used. The capacity of the unit at a speed of 50 fpm is approximately 30 tph per inch of width at peak loadings, average capacity being about 1/3 of peak loading. The assembled conveyor is shown in Fig. 5, with views of both the top and the underside to show all the construction details. In particular, the following general design principles were carried out in this construction:

Jan 1, 1954

By J. Szekely, P. Tarassoff, N. J. Themelis

In a copper converter air enters the bath in the form of turbulent jets. The interaction of these jets with the molten matte is fundamental to the converting process. In the present study, an equation is derived to describe the trajectory of a gas jet in a liquid. Calculated and experimental results for air jets injected into water are in good agreement. The trajectories of air jets in copper matte are predicted. THE air injected through the tuyeres of a Peirce-Smith copper converter emerges into the bath of molten matte in the form of a highly turbulent jet. The air jets affect a number of chemical and physical processes occurring in the converter: i) Converting Rate. It is generally recognized that the production capacity of a converter is limited by the flow of air which can be injected through the tuyeres and by the oxygen efficiency. In turn, the air flow is limited by pressure drop considerations or by the amount of splashing within the converter. ii) Oxygen Efficiency. This depends on the dispersion of the air jet in the liquid bath, and its trajectory through the bath. iii) Mixing. The jets act as mixing devices by transferring momentum energy to the bath; in this way the heat generated by the converting reactions occurring in the jets is distributed through the bath. iv) Refractory Wear. The proximity of the jets, which are centers of heat generation, to the refractories in the tuyere zone may have an important effect on refractory life. Mixing conditions in the bath will also influence refractory erosion. v) Splashing, and Accretion Build-Up. The energy of the jets is not dissipated entirely in mixing the bath. particles of liquid are carried out kith the gas above the surface of the bath in the form of liquid spouts and droplets. These result in the undesirable build-up of accretions on the converter mouth, and dust losses in the flue gas. Despite the importance of the interaction of the air jets and the matte in a converter, very few studies of the fluid dynamics of converting have been reported in the literature. Metallurgists in the USSR appear to have been more concerned with the subject than their Western counterparts. Deev et al.1 studied the interaction of an air jet with aqueous solutions in a converter model and qualitatively determined the tuyere air velocity and tuyere inclination which produced the most favorable results with respect to good mixing in the bath, and minimum splashing. Shalygin and Meyer-ovich2 also examined the air-matte physical interaction both in models and in industrial converters; they concluded that in conventional converting practice, there was no significant penetration of the air jets into the matte layer, and consequently the converting reactions occurred mainly in a zone adjacent to the tuyeres. The behavior of air jets in a converter bath, and the aerodynamic characteristics of tuyeres are discussed at length in a monograph on converting by Shalygin.3 However, the description of the phenomena occurring in the converter bath is largely qualitative. The side-blown Bessemer converter for steelmak-ing is very similar to the Peirce-Smith copper converter. Among the few investigations of the behavior of air jets in the bath of a Bessemer converter are those of Kootz and Gille4 who studied splashing in the course of an investigation on the effect of blowing conditions and converter shape on nitrogen pick-up in Bessemer steel. They found that during blowing standing waves were formed on the surface of the bath; the amplitude of the waves increased with the depth and angle of tuyere immersion until the whole bath moved backwards and forwards causing heavy splashing. Kazanstev5 used a model of a Bessemer converter to obtain correlations between the axial velocity of a gas jet and distance from the tuyere orifice and the Froude number of the jet. shalygin3 used these results to calculate the horizontal penetration of an air jet in a copper converter; the penetration was defined as the distance in which the axial jet velocity decreased to 10 pct of its initial value. However, the rising trajectory of the jet was not taken into account. In the absence of quantitative information on the fluid dynamics of converting, the design of copper converters has been based mainly on operating experience. Such experience tends to vary widely from smelter to smelter., This is reflected in Table I which is based on data compiled by Lathe and Hodnett.6 Aside from a rough, and perhaps obvious correlation between the total air flow and converter volume, Fig. 1, no pattern emerges from the data. For example, tuyere throat air velocities vary from 215 to 465 ft per sec in converters of the same size, for little apparent reason. The air jet energy input per cubic foot of converter volume, which may be taken as a measure of the amount of mixing in the converter bath, also varies greatly. A recent analysis of converter data by Milliken and Hofinger7 has also revealed unexplained variations in operating parameters. It is believed that by gaining a better understanding of the fluid dynamics of converting a more rational basis may be provided for the design of converters. In particular, it is proposed that if one takes into account the desirable criteria of a high converting rate, high oxygen efficiency and long refractory life, there should be an optimum configuration of tuyere air flow for a converter of a given diameter. The present investigation is concerned with the form and trajectory of an air jet in a converter bath. The general theory of turbulent jets has been expounded by Schlichting8 and Abramovich.9 However, most experi-

Jan 1, 1970

By C. W. Merrill

The price records of seven representative mineral commodities for the 68-year period 1890 through 1957 have been compiled and analyzed for significant trends. When these records are reduced to real prices in terms of dollars of constant purchasing power or to the purchasing power of industrial wages at average rates, a substantial overall fall in prices is revealed. This downtrend contradicts the widely held concept that heavy drafts on a mineral resource must lead to scarcity, reflected in rising prices. Three metals (aluminum, copper, and pig iron), two fuels (bituminous coal and petroleum), and two nonmetals (sulfur and cement) have been chosen because of their pre-eminence in their respective categories, their significance in an industrial economy, and the ready availability of their price records. It might be added that these seven commodities were selected before any price figures were compiled; none was selected or rejected to substantiate any preconceived notions as to price trends. The overall importance of the seven is demonstrated by the fact that, taken together, they composed over three-fourths of the value of all minerals produced in the U. S. in 1957. The first step in the analysis was to reduce the price records to a basis for significant comparisons. Two such comparisons have been made: 1) The quantities of each of the commodities that could have been purchased for an average hour's wage in each year, and 2) the unit price of each commodity through the years in terms of deflated dollars. These data are set forth in the accompanying table and two charts. The quantities of the mineral commodity purchasable with the average wage for one hour's work in all manufacturing industries through 1926 were based on annual average prices and on average annual wage rates determined by Paul H. Douglas and published in his "Real Wages in the United States, 1890-1926." The series was extended through 1957 by the Bureau of Labor Statistics, U. S. Department of Labor. Calculations based on these data show that the average worker could have purchased 1.28 lb of copper with his hourly wage in 1890, whereas his hourly wage would have purchased 8.11 lb in 1957, an increase of 633 pct in the 68-year period. An average hour's wage would have bought 10.85 gal of petroleum in 1890, compared with 33.04 gal in 1957. Even more spectacular is the increase in sulfur, of which 25.25 lb could have been purchased with the 1904 average hourly wage; 223.08 lb were purchasable with the wage in 1957—an increase of 883 pct. Comparable price data for sulfur are not available for years earlier than 1904. For every commodity, the calculations show an improvement in the wage earner's purchasing power in 1957 compared with the early years. Measuring purchasing power in terms of wages does not give an entirely fair picture of the availability of a commodity in an economy. When the efficiency of an economy changes and the balance shifts among such elements as raw-material production, manufacturing, and service trade, the economic significance of an hour's work changes. Partly to meet such criticism, but mostly to present another interesting measure of the response of minerals to changing market conditions, a second set of calculations has been made to deflate unit prices for the seven commodities into terms of 1954 dollars. To accomplish this adjustment to a common 1954 parity, the Gross National Product Price Deflator, developed by the Office of Business Economics, U. S. Department of Commerce, was used. Although the results of these calculations are not as striking as those based on labor's increasing purchasing power, nevertheless the declines outweigh the rises in the prices of the mineral commodities. In terms of these deflated prices, aluminum and sulfur are much cheaper today than in the early years; copper was substantially cheaper in 1957 than in 1890; pig iron and petroleum are little changed; and only bituminous coal and cement have increased substantially. Strangely, the two mineral commodities with the strongest reserve positions are the two to exhibit rising real prices. Now this apparent overall downtrend in prices has taken place during a period of almost fantastic increase in the demand for mineral products. The value of minerals consumed in the world during the period greatly exceeds all mineral consumption up to 1890. A stage has been reached in the U.S. in which 95 pct of the energy used is of mineral origin and in which machines, structures, roadways, communication facilities, and most other elements in the industrial economy are primarily of mineral origin. Even agricultural fertility is maintained, in large measure, by mineral fertilizers. A series published in Minerals Yearbook shows that the value of U. S. mineral products has risen from $615 million in 1890 to $18,000 million in 1957, a 29-fold increase. Even in deflated dollars, the increase has been eightfold, while population has expanded less than threefold. Not only are demands of the industrial nations— the U. S., countries of Western Europe, and Japan— increasing at rapid rates, but those countries with agrarian economies are calling themselves underdeveloped and clamoring to industrialize. The ever-expanding mineral requirements in the U. S. and throughout the world show no abatement. Mineral reserves frequently have been described as wasting assets. Much concern has been shown for future users, who have been pictured as finding themselves on a plundered planet. Conservationists have viewed the future with alarm and have demanded legislation and regulations to reduce the drain on mineral reserves.

Jan 1, 1960

By Charles S. Barrett

THIS paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstructures. About 12m exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,1 and a number of these have been selected to illustrate the results obtained. Prints are also included showing the common types of falsities-to borrow a term from the biological field, the "artifacts." In brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. n addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains. Since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. SPECIMEN PREPARATION AND PHOTOGRAPHS Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for repeated polishing and etching (each successive polish becoming less severe and each etch lighter), since the final etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and IC, the replicas used were of silica, deposited up0n polystyrene and floated from the polystyrene in ethyl bromide according to polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1943

By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943