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By J. S. Woodward, F. B. Plummer

The measurement of the rate of flow of liquids through sands dates back to 1856, when H. d Arcyb, a French physicist, carried out his classic experiments on the flow of water through sand layers. The earliest recorded data on relationships of pressure to flow of fluids through porous rocks in this country are those of Newell 23 in 1885. The first comprehensive studies of flow were made in 1898 by King15, who measured the rate of flow of water and air through consolidated and uncon-solidated sands and published the results. From 1900 to 1920 there appears to have been little interest in permeability. In 1920 the increase in demand for oil led the U. S. Bureau of Mines to begin a series of experiments to determine subsurface relationships of oil and water and the characteristics of their flow. Mills18 studied the relationship of flow of liquids to text- and structure of the sands, and Melcher17 in 1925 made a quantitative study of effect of changes in pressure on rate of flow of crude oil through Oklahoma oil sands. Since 1930 the importance of flow measurements to production of oil and gas has been emphasized by a large number of excellent investigations. Among these the works of Fettke9.10, BarbI.2, Cloud6, Nutting24-", Bot-set4, Nevin22, Tickell32.33, Fancher, Lewis and Barnes8, Moore, Schilthuis and Hurst19, and Wyckoff, Botset and Muskat"-39 have contributed much to our knowledge of the technique of permeability measurements and to the laws of liquid and gas flow through porous sands. The application of their work has led to the establishment of laboratories for measuring the permeability and porosity of oil sands by most of the large companies. All the investigations, except those of Wyckoff, Botset and Muskat, and Moore, Schilthuis and Hurst deal with linear flow; that is, flow in a more or less straight line through a given cross-sectional area of sand. Three years ago, at the University of Texas, experiments were started to measure radial flow of liquids through sands; that is, flow from all directions toward a central opening—the conditions that operate in a

Jan 1, 1937

By E. D. Gardner

INTRODUCTION OIL shale deposits have been exploited in various countries throughout the world, but generally with government aid. The oil-shale industry of Scotland perhaps is the oldest and best-known; the largest was conducted in Manchuria by the Japanese during World War II as a source of liquid fuels for military uses. In general, foreign oil-shale deposits that have been exploited are much lower grade than those in the western United States. Considerable interest began to be shown in western oil shales in 1916; the peak of activities was in 1923. The Catlin operation, near Elko, Nevada, perhaps was the nearest approach in this country to an oil-shale enterprise on a commercial scale. Over 100 companies were formed, ostensibly for exploiting the oil shale; a large number of them, however, proved to be stock promotions only, which gave the embryo industry a black eye. The Bureau of Mines operated an experimental oil-shale retort plant near Rifle, Colorado, from September 1926 to June 1927 and again from April 1928 to July 1929, after which the plant was dismantled. By this time the East Texas oil fields had come in and the country lost interest in substitute liquid fuels. During World War II the Nation again became concerned about the magnitude of its petroleum reserves. Congress (April1944) directed the Bureau of Mines to build and operate demonstration plants to produce synthetic liquid fuels from coal, oil shales, and agricultural and other products; a five-year program was authorized. As a part of this program the Bureau of Mines has built, at Anvil Points near Rifle, Colorado, a retort plant and developed an experimental mine to supply the plant with oil shale. An important part of the mining work at Rifle is to devise methods and select practices for mining the oil shale on a commercial scale at the lowest practicable cost. The product to be mined has a relatively low value, a fact that must be kept continuously in mind. The combined aim of those in charge of the mining and those in charge of retorting is to demonstrate that the shale oil can be produced at a cost per barrel corresponding to the current quotation for crude petroleum -or at least very close to it. Plans call for an uninterrupted flow of broken oil shale from the face in the mine, through crushers, through the retorts and thence to the disposal dump. The disposal of the spent shale in the Rifle area should present no unusual problem. Mining research has consisted so far of paper studies of the general phases of the problem, determination of the widest span that the roof stone will stand safely unsupported, and drilling problems. Underground development has not proceeded far

Jan 1, 1947

By David P. Hale, Guy W. Jordan

High-iRon cements have a number of advantages over cements carrying little or no iron. The presence of iron in Portland cement aids in the manufacture of the cement and also imparts certain advantageous physical properties to the finished product. In manufacture, the presence of iron lowers the fuel consumption, increases the ease of proper"burning, and lessens the destructive action of the charge on the kiln refractories. In the finished cement the presence of iron reduces the expansion and contraction, adds strength, adds increased resistance to"freezing and thawing, and increases the resistance of the cement to sea "or sulphate waters. [" During the past few years the construction of numerous dams through- "out the Southeast by the Tennessee Valley Authority has stimulated the "production of high-iron cements. At present a great number of specifica- "tions call for an iron cement, and the industry is supplying this demand "with a Portland cement carrying approximately 5 per cent iron oxide. "Several manufacturers are now making practically all of their cement "of this type and a number of others manufacture it as a special cement "over short periods to meet demands from the Tennessee Valley Authority "and other buyers. " The recent increase in the use of iron in Portland cement has created "a market for iron products that previously was nonexistent. The chief "sources of supply for the cement manufacturers at present are iron sand, "iron sinter and slag, and ocher. The Copperhill mining district, Ten- "nessee, supplies both iron sinter and slag for use in cement. The Carters- "ville district supplies iron sand, ocher, and some iron resulting from the "magnetic separation of iron from barite. The advantages of these "products vary according to the chemical properties of the raw materials "and the methods of handling used by the different manufacturers. Where "the iron is to be handled by conveying belts and in hopper cars, the iron"sand and sinter and slag are preferable. Where the silica content must "be raised, the iron sand is doubly advantageous because it supplies both

Jan 1, 1942

By J. L. Rodda

THE desirability of a uniformly sized abrasive for metallographic polishing has probably been recognized in a general way for a long time. Certainly all metallographers have recognized the damage that can be done to a polished surface by a piece of grit, especially if one of the softer metals, such as zinc or aluminum, is being polished. It is to be doubted, however, whether many metallographers have had any adequate idea of the particle size of the abrasives they were using or of the range of sizes encountered in any given grade of abrasive. At any rate, the descriptions of abrasives for metallographic work found in the literature are generally very meager. It was with the idea of securing an abrasive with a limited range of particle size that a study of this problem was commenced. Commercial abrasives, even when recommended for metallographic work, are made up of particles of varying sizes. One such abrasive contains some particles so fine that they remain in suspension for days and other particles so coarse that they settle at the rate of 3 in. per minute. It is evident that the coarsest particles are over 100 times the diameter of the smallest ones, or over 1,000,000 times the volume. The hopelessness of avoiding scratches under these conditions is evident. Vanderwilt1 has described a laboratory method for grading abrasives in which the elutriator is used. Le Chatelier's method, described by Goerens,2 also makes use of an elutriator. However, the elutriator is too slow for this purpose and requires too delicate a control for the range of sizes desired. The method of stirring up the abrasive in water, allowing it to settle for as given time, then drawing a measured depth off the top of the suspension, has been finally adopted as the simplest proce-dure. The largest particle in a given portion is. then determined by Stokes' law:3

Jan 1, 1931

By R. N. Bhattacharyya

In recent years, increased attention is being paid to the application of oil-agglomeration technique for (a) improved recovery of low- ash clean coal, (b) effective beneficiation of low-grade coking coals and (c) removal of pyrite sulphur from high-sulphur coals. In this technique, which has been proved to be more effective than convention- al froth-flotation, advantage is taken of the oleo-philic nature of finely ground coal to separate it under controlled conditions from the associated minerals which are hydrophilic in nature. Unlike froth- flotation, no aeration is needed in the process and the concentrates which are obtained in the form of agglomerates or micro-pellets have easier dewatering characteristics. Optimization of operating variables in treating individual raw feed is a pre-requisite for the successful application of this process. A 10 gram batch unit was employed in the present test series. This paper presents - results from these investigations on such operating variables as (i) size of coal, (ii) amount of oil used, (iii) time of stirring, (iv) rate of stirring, (v) solid content in slurry and (vi) effect of conditioning.

Jan 1, 1977

Some coal was mined in this area under lease from the Indians before it became a state. Table 75 shows all production figures available. [ ]

Jan 1, 1942

By P. E. McKinney

Developments in engineering during the past decade, particularly as applied to marine construction, mining machinery and other purposes in which corrosion offers a serious problem, have created a large demand for a non-ferrous metal highly resistant to corrosion and at the same time useful in general construction work as a substitute for steel without materially decreasing the factor of safety or increasing the weight of the various parts over that ordinarily used in the case of mild steel. To obtain the combination of desired properties many compositions have been proposed and used with excellent success, but at the present time probably the most popular and most widely used combination is the non-ferrous alloy commonly called manganese bronze. This is nothing more than a high brass to which have been added, by the proper method of alloying, comparatively small percentages of aluminum, iron, or manganese with the definite purpose in view of strengthening the alloy and rendering it more dense and close-grained than the average yellow-brass casting. In the manufacture of manganese bronze a great deal has been said about the importance of using only the highest grades of raw material and the beneficial or detrimental effects, as the case may be, of various impurities, as well as the importance of adding the ingredients according to various formulas proposed; but in most of these cases the literature on the subject has dealt principally with the manufacture of this alloy from virgin metals and raw materials of the highest purity. It is the purpose of this paper to deal particularly with the possibilities that lie in the proper development of methods for manufacturing such an alloy by more economical methods than those which have usually been discussed in other literature on the subject. Shortages have recently existed in raw materials needed for many products entering into the various branches of engineering work, particularly the non-ferrous metals, and during the next few years of reconstruction the country will be flooded with many

Jan 1, 1919

By J. R. Ross, J. B. Rosenbaum

Bureau of Mines research has resulted in the development of fluid- bed ion-exchange columns for recovering uranium from slime pulps. In pilot plant tests, slime slurries containing up to 6 percent solids were processed at flow rates of 10 gallons per square foot per minute with high uranium recoveries and efficient resin loadings. Uranium was effectively eluted in a laboratory fluid-bed elution column at eluate-to-resin ratios of less than 5:1 and eluate flow rates of 3 gallons per square foot per minute. Construction costs of mills using these improved ion exchange techniques are estimated to be 25 percent less than for mills using solvent extraction of clear solutions. For mills having a capacity of 2,000 to 2,500 tons of ore per day, the saving would be in the range of $2.5 million. In addition, a saving of about $0.80 per ton of ore in total operating costs is indicated.

Jan 1, 1973

The stabilization of a gravel road with soil is a method of treatment developed in recent years by the United States Bureau of Public Roads for the purpose of binding the constituents together better, and maintaining a more durable surface. The process consists in adding to the gravel or crushed stone and sand, a soil mortar, so-called, of fine sand, silt and clay, mixed in the proper proportions. The coarse gravel and sand supply structural strength and hardness; the fine sand adds embedment support to the coarse sand; the silt acts as a filler to prevent the granular particles from rocking; while the clay serves not only as a binder but also provides pores minute enough to cause connecting moisture films which are supposed to have high cohesive properties'. It will be recognized that the clay is an important ingredient both when wet and dry, and should not show excessive expansion when wet, nor correspondingly high shrinkage in drying, as otherwise there is danger of unseating the nonplastie particles. Such a stabilized road, although an improvement on one with a floating surface, will in course of time be subject to wear, and become dusty when the clay dries out and breaks up. It has been found that if some salts are added to the road mixture they tend to maintain the soil moisture and prevent dustiness of the road or raveling of the road surface. In addition to this, it is claimed that these dissolved salts cause a thinning of the moisture films on the particles, thus permitting greater compaction of the road mixture, and thereby increasing its density. This fact can be proved by noting the increased compaction which a road mixture shows when certain salts are added to the soil water. Since certain chemical substances such as sodium chloride are electrolytes, the question arises whether they cannot have wine effect on the qualities of the clay in the soil mortar, and perhaps improve them. In view of the fact that certain salts seem to exert a favorable effeet on the road mixture it is desirable that they he held in the road soil as long a time as possible.

Jan 1, 1938

By H. R. Hanley

The characteristics of alloyed anodes and their influence on the products of electrolysis and power consumption have been noted previosly ously in the literature.' This paper presents data in continuation of the subject given in an earlier paper by the authors.2 As noted in the authors1 previous paper, the objectives of this work are the reduction in the cell voltage and the purity of the cathode product resulting from the use of alloyed lead anodes. The fundamental facts developed in the previous paper were: (I) that the presence of a small amount of calcium lowers the anode potential approximately 50 per cent. below that of pure lead; and (2) that thallium when present to the extent of 4 per cent. rendered the anode practically stable, thereby lowering the contamination of the cathode by lead to a very insignificant amount. The specific features determined in this recent work are as follows: 1. The lowest limit of calcium in the lead which will still give maximum lowering of the anode potential. 2. The characteristics of the thallium-calcium-lead anode. 3. The characteristics of the silver-calcium-lead anode. 4. The characteristics of the thallium-silver-calciurn-lead anode. It was determined that 0.1 per cent. calcium in the anode was sufficient to lower the anode potential approximately 50 per cent. Table 1 shows the characteristics of alloyed anodes tested. The anode composed of 0.1 per cent. calcium, 4 per cent. thallium, and 95.9 per cent. * Professor of Metsllurgy, Missouri School of Mines. t Professor of Metallurgy and Ore Dressing, Hea.d of Department, Missouri School of Mines. Assistant Professor of Metallurgy, Missouri School of Mines. 1 Among others, see C. G. Fink and Li Chi Pan: Insoluble .Anodes for the Electrol-ysis of Brine [Trans. Amer. Electrochem. Soc., (1926) 49, 83-1341 and other papers by these authors. U. CJ. Taintori, 8. G. Taylor arid H. P. Ehrlinger: Lead Alloys for Anodes in Electrolytic Production of Zinc of High Purity. Truns. A. I. M. E. (1929) 192-200. 2 H. R. Hanley, C. Y. Clayton, D. F. Walsh: Investigation of Anodes for Production of Electrolytic Zinc. Trans. A. I. M. E. (1930) 275

Jan 1, 1931

By Chester W. Washburne

At present it is impossible to estimate closely the amount of oil obtainable from a given area of land. However, after the completion of a few properly distributed prospect wells, one can calculate the approximate yield of the sands penetrated, with a probable error of say 50 per cent. Even rough predictions of this kind are of value in large operations. Without wells upon it, one can never be absolutely certain that an area will produce any oil whatever, and one can only indulge in wild guesses of the probable productive area, before the geological structure has been carefully contoured and the top of the basal water plotted on a map. This requires wells. At times it is desirable to form an idea of the possible yield of oil in advance of drilling, as in cases where the price asked for undeveloped land seems too high, but where the probability of finding oil is furnished by neighboring development, supported by the geology. In such cases the most one can do is to make an estimate of possible maximum yield, which may of course far exceed results, and which is of use mainly in the prevention of excessive initial investment. The method is very significant in a general way, as in regions like the Bighorn Basin, Wyoming, where the productive sands in the Cretaceous shale are so few and so thin and fine that they cannot develop very great production, although the high quality of the oil probably will counterbalance this defect sufficiently to give local profit in favorable areas. Reservoir Capacity of Sands.—The porosity of a stratum is the measure of its maximum reservoir capacity for liquids and gases. The porosity may be determined experimentally and must be used in connection with the total volume of the sand.

Jan 1, 1915

By John B. Mertie

MONAZITE formerly was described as moribund, but, in the light of recent developments, it is no longer so. It is the common source of the rare earths and thorium, both of which are becoming progressively important in industrial and other applications. Moreover, by the action of foreign governments, the sources on which the United States has depended for its supply are now either restricted or cut off entirely. Monazite has thus become a scarce mineral and processors in this country are endeavoring to acquire it from all available sources. RARE EARTHS AND THORIUM The rare earths proper, as defined by spectroscopists, are the oxides of cerium, praseodymium, neodymium, prometheum, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium, with atomic numbers ranging respectively from 58 to 71. Chemists include with the rare earths scandium, yttrium, and lanthanum, with atomic numbers respectively of 21, 39, and 57. Thorium, with an atomic number of 90, is analogous to lanthanum, in that it precedes a second group of elements, whose oxides constitute the "rare earths of higher order." These are protactinium, uranium, neptunium, plutonium, americium and curium, with atomic numbers ranging respectively from 91 to 96. The last four mentioned are artificially prepared elements that so far have not been detected in nature. The rare earths with odd atomic numbers, except europium and lutecium, have no natural isotopes; and the two exceptions have only two isotopic forms. Those with even atomic numbers have from 4 to 7 natural isotopes. Samarium148 is radioactive, disintegrating over a half- life of 1.4 X 10 11 years with the emission of alpha rays. Lutecium176 is weakly radioactive, disintegrating over a half-life of 2.4 X 1010 years, with the emission of beta and gamma rays. At least 64 radioactive isotopes of the rare earths proper have been artificially prepared. Thorium is a strongly radioactive element, with a half-life of 1.39 x 1O10 years, which disintegrates through a series of 14 isotopes of 10 elements. The two longest lived and most important of these are

Jan 1, 1949

By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By W. A. Backofen

THE texture of cold-drawn copper wire has been described most often as a composite of [Ill] and [loo] directions aligned parallel to the wire axis.' Hibbard2 suggested that sufficient reduction will result in a single [111] texture and reported that after a reduction in area of 96.4 pct, such a texture was nearly obtained. Other work3-4 has shown that recrystallization within the temperature range of 300" to 1000°C does not alter the texture established by cold-drawing. In general, however, the texture of cold-drawn end annealed copper wire is not as well defined as the deformation texture. In the work reported here it was found that the double-fiber, deformation texture persists even after a reduction in area of 97.3 pct, and after recrystallization the texture is practically all [l00]. The wire used in this work was prepared in the following way. A 3/4-in. diam length of annealed OFHC copper was cold-drawn to a diameter of 1/8 in., a reduction in area of 97.3 pct. Each step in the drawing operation brought about a reduction in area that varied from 6 to 10 pct. Short lengths of this wire were etched in a 50-pct solution of nitric acid to a diameter of approximately 0.01 in. The texture of the cold-drawn specimens was determined with the conventional X-ray transmission diffraction technique using filtered copper radiation. The X-ray beam was directed perpendicularly to the wire axis and the diffraction rings were recorded on a flat film. Fig. la is typical of the photo-grams obtained and reveals that the cold-drawing schedule described above introduces a distinct, double-fiber texture with both [Ill] and [l00] directions aligned parallel to the wire axis. Supplementary measurements with a Geiger-Mueller counter of the intensity of reflection from (111) planes showed that the [111] component was much more predominant than the [l00]. Additional specimens of the drawn and etched wire were annealed in a salt bath at temperatures from 300" to 450°C. The texture of the recrystal-lized wire was studied with the same technique applied to the cold-drawn wire. Fig. lb is an X-ray photogram of a specimen annealed for 1 ½ at 300°C and is typical of those obtained from re-crystallized specimens. The photogram shows that recrystallization of this material is accompanied by the almost complete elimination of the [111] component of the deformation texture. A pronounced strengthening of the [100] component was evident from intensity measurements with a Geiger-Mueller counter. In summary, the deformation texture of cold-drawn OFHC copper wire, after a reduction in area of 97.3 pct, may still be described as a composite of [Ill] and [loo] directions aligned parallel to the wire axis. Recrystallization of such wire at temperatures from 300" to 450°C introduces a texture which consists almost entirely of a [loo] alignment. Acknowledgment Sidney Rolle of the Scomet Engineering Co. generously supplied the OFHC copper used in this work. References 'C. S. Barrett: Structure of Metals. p. 382 (1943) New York. McGraw-Hill Book Co. 2 W. R. Hibbard, Jr.: Trans. AIME (1949) -185, p. 598; Journal of Metals (Sept. 1949) TN 19E. 3 P. 422 of ref. 1. 'E. Schmid and G. Wasserman: Ztsch. Physik (1926) 40, p. 451.

Jan 1, 1952

By P. A. Boeck

(San Francisco Meeting, September, 1915) THE thermal insulation of high-temperature equipment for industrial purposes is a subject that has not received from engineers and designers the attention its importance deserves. This may be attributed to a number of causes: In the first place, heat flow is a rather difficult factor to measure under the working conditions of an industrial furnace, and until the comparatively recent introduction into certain operations of the heat balance sheet, with a systematic attempt to account for the discrepancies in the totals, the various causes of heat losses and the reasons for their existence were not brought to light. Moreover, such rapid advancement and radical changes in the design of equipment, especially in metallurgical lines, have occurred that practice has apparently outdistanced the theory of design. In the modern tendency toward greatly increased size of units, effort has seemingly been made to utilize the heat of fuel gases without proper. attention having been paid to conserving heat energy and confining it strictly to the points of maximum activity. The systematic study of the thermal properties of structural materials, which is being carried out by various government bureaus and also by a number of technical societies, is forming the basis for more intelligent and consistent work in the economically important subject of prevention of fuel waste.

Jan 8, 1915

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By Robert B. Sosman

THE chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily smaller. I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting on a paper that I had recently published27 on "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of Professor Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. SCOPE OF THE LECTURE During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyrometric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the United States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the "temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that "temperature of the furnace" is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1948

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.' on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-' (g S per sq cm)' corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.' The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By Edward Gridley

At the meeting of the Institute, held at Roanoke, Va., in June, 1883, I gave some facts in relation to charcoal pig iron of unusual strength, made from our carbonate ore taken from the mine at Amenia, N. Y. My object in again bringing the subject to the attention of the Institute, is to obtain, if possible, the solution of a prohlem in connection therewith. Our furnace is of the old type, stone stack 32 feet high by 9 feet 2 inches at top of bosh; bosh about 67O pitch; stone hearth; three tuyeres of 31/4-inch opening; fuel, a mixture of hard and soft coal; blast about & to # pound pressure, and heated to 400' to 600° Fahr. by iron pipe oven on top of stack. The analysis of the roasted carbonate ore, as before given to the Institute, is as follows:

Jan 1, 1884

By R. F. Mehl, A. H. Geisler, S. Barrett

The studies of the mechanism of pre= cipitation and of the resulting property changes in aluminum-silver alloysl-3 have presented some new concepts of the aging reactioxl—concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.l,4 These platelets grow in lateral dimensions and in thickness with aging time until they arc thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstatten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuoils precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 Expermental Procedure The alloys were made using 99.97 per cent A1 or distilled magnesium, with

Jan 1, 1943