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By Paul M. Tyler, Colin G. Fink

THE field of rare metals is so broad that progress can be reported upon many important fronts. Not satisfied with the 92 elements that Mendeleeff and his followers have accepted as legitimate, scientists are trying now to complicate matters by making new elements. Enrico Fermi announced the fabrication of "Element 93". Uranium, instead of being allowed to disintegrate slowly according to its normal habit, was bombarded with neutrons until some of them seemed to have stuck in the nucleus. To understand just what is alleged to have happened all one has to do is to line up the elements in their usual order of ascending atomic weight and imagine, as physicists do, that each atom is a little solar orbit comprising a central mass or planet about which other masses revolve like satellites. Ordinary hydrogen, being very light, consists of only one positively charged proton center, with only one positively charged electron revolving about it. Other atones are progressively more complicated until we come to uranium, which has a relatively big center and 92 particles revolving around it.

Jan 1, 1935

By David B. Reger

New discoveries of gas in the southern counties featured the petroleum industry in West Virginia during 194;. Drilling for oil increased slightly over 1944 and a small increase of initial production resulted. Out of 28 wildcats drilled, there were 16 gas discoveries and 12 dry holes. No commercial oil was found in the 28 wells.

Jan 1, 1946

By K. H. G. Ashbee, J. W. Heavens

One consequence of the distribution in orientation of Bragg diffracting planes in an elastically bent foil is that simultaneous diffraction occurs from ±g pairs, where g is the reciprocal lattice vector to a diffracting plane. If such Bragg contour pairs are indexed, then the variation in orientation with respect to the incident electron beam is known. This note describes a construction by means of which Bragg contour pairs may be indexed by inspection. Referring to Fig. 1, the Ewald sphere radius is l/h, where is the wavelength of the electron beam, and the half spacing of first-order reciprocal lattice planes is l/d, where d is the corresponding spacing in direct space. The angle subtended by the zero and first-order planes at the center of the Ewald sphere is a = sin-' Thus, to represent a pair of first-order Bragg contours on a stereographic projection, measure ±a from, and along the normal to, the zero-order plane. The traces of the required Bragg contours pass through these points and parallel to the zero-order trace. In practice, it is desirable to enlarge a stereographic projection of the zero-order planes before making the construction. As an example, a stereographic projection of first-order Bragg contours up to line 27 for an fcc crystal is given in Fig. 2; if required, higher-order contours can easily be added. Fig. 2 is, of course, a map of first-order Brillouin zone boundaries. One use of this construction is the measurement of large elastic fields in electron microscope specimens. Fig. 3(a) shows a pattern of Bragg contour pairs due to lattice distortions near a large precipitate. This particular example is of a T-phase precipitate in Hidu-minium 54 (A1 + 6 wt pct Cu, 0.5 wt pct Mn). Foil buckling is produced by annealing during observation and may be evidence for evaporation from the precipitate.' Comparing Figs. 2 and 3(0), it is evident that the axis of high symmetry in Fig. 3(a) is [lll]. The strain in a bent foil is approxinlately t/2r, where / is the foil thickness and ? the radius to which the foil is bent. From the projections of grain boundaries and of helical dislocations, it was estimated that ( - 3000A, and values for ? were obtained from the

Jan 1, 1968

By J. A. Fellows, Earnshaw Cook, H. S. Avery

THE increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni, 16 per cent Cr, 35 per cent Ni, 12 per cent Cr, 60 per cent Ni, etc ) in recent years has been accompanied by continued demands by the consumer for improvement in properties The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloy presented in a companion paper† The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized THE CREEP TEST Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure The creep-test laboratory constructed for the American Brake Shoe and Foundry Co is designed to permit 1000-hr tests in the temperature range of 1200° to 2200°F with a choice of applied stress extending from 50 to 50,000 lb per sq in in increments of 50 lb per sq in To simplify the calculation of weight combinations, the loading beams (Fig I) are provided with counterweights to eliminate the tare The precision of the knife-edges (10 1 ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a 1-gram weight attached to the loading shackle Check of the loading weights proved the maximum error to be 0 06 per cent Axial alignment is provided by crossed knife-edges in the grip seats The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U S Steel Corporation An 80 per cent Pt, 20 per cent Rh No 19 B and S gauge wire is used as the heating element The details of construction are shown in the radiograph reproduced in Fig 2 The windings are held in place on an alundum tube with alundum cement, the distribution of turns is adjusted to give a maximum temperature gradient of ± 1°F over a 4-in gauge length (Fig 3) To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length Sixteen-inch coupons are used to reduce the temperature of the threaded

Jan 1, 1942

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By AIME AIME

THE John Fritz Gold Medal for 1929 was presented to Herbert Hoover at the Executive Mansion on April 25, at a luncheon given by Mr. Hoover to present and past members of the Board of Award, preceding medalists, and presidents and secretaries of the American societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers. The presentation party of forty engineers which gathered at the White House, from all parts of the United States, was made up of past presidents of the four senior national engineering societies that established the John Fritz Medal and included five men who had received the medal in previous years. These former medalists were Edward Dean Adams, J. J. Carty, J. Waldo Smith, Elmer A. Sperry and Ambrose Swasey. This medal is the highest honor bestowed by these four national engineering societies, having a membership of 60,000. It is awarded not oftener than annually for "notable scientific or industrial achievement, without restriction on account of nationality or sex." In accordance with custom, the award to Mr. Hoover was made tentatively and without announcement in October, 1927, and was formally con- firmed and announced one year later.

Jan 1, 1929

C. R. CORNING, Chairman. ADOLPHE E. BORIE, First- Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. Vice-Chairmen. JOHN H. ALLEN, GEORGE M. COLVOCORESSES, RICHARD M. ATWATER, JR., -ROBERT PEELE, GEORGE D. BARRON, CHARLES P. PERIN, A. CHESTER BEATTY, JOSEPH A. VAN MATER, J. PARKE CHANNING, ARTHUR L. WALKER. D. C. Bard, Howard Eckfeldt, Milton H. McLean, W. de L. Benedict, R. C.Gemmell, ' Philip N. Moore, John C. Branner, F. Louis Grammer, T. H. O'Brien, Palmer Carter, Ernest A. Hersam, James J. Ormsbee, Allan J. Clark, Edwin C. Holden, Edward W. Parker, F. Crabtree, William L. Honnold, John B. Porter, George G. Crawford, Reginald E.. Hore, R. M. Raymond, O. C. Davidson, C. Colcock Jones; Robert B. Richard's, E. V. D'Invilliers, Eugene P. Kennedy, LeRoy Salsich, James S. Douglas, Chester F. Lee, Henry L. Smyth, Walter Douglas, Richard S. McCaffery, F. W. Traphagen, Howard N. Eavenson, James F. McClelland, Elton W. Walker. Meetings of this committee were held at the Institute headquarters on April 18, May, 3 and 15, and June 19.. At the meeting of June 19, the Secretary reported that letters of invitation to apply for membership in the Institute had been sent to all the alumni of the School of Mines of Columbia University and also to all State Mine Inspectors and their deputies. He also reported the securing of lists of the alumni of the Harvard Engineering Schools, and of the Mining Schools at Houghton, Mich. ; Butte, Mont. ; State College, Pa. ; Seattle, Wash. ; Fayetteville, Ark.; Laramie, Wyo.; Montreal, Canada, and Wor-cester and Rensselaer Polytechnic Institutes. Arrangements were made to invite all these to join the Institute. It was suggested that a. member' of the Institute resident in Australia be appointed to this Committee, also one from Japan. Attention of the members of the Committee was drawn to the fact that letters requesting, others to join the Institute will be written in the offices of the Institute if desired. The applications for membership received recently have been as follows March, 30; April, 02; May, 70; June, 54. The next meeting will be held July 17. THOMAS T. READ, Secretary.

Jan 7, 1913

Joseph W. RichaRds, South Bethlehem, Pa. (communication to the Secretary*): The hold experiment of Mr. James Gayley in drying the blast used in the Isabella furnace has attracted the attention of the whole metallurgical world, and has given rise to a wide discussion of the reasons for its great success. Mr. Gayley and the capitalists who backed him in his work deserve congratulations on the success of the venture, not only because it succeeded, but because they have been rewarded far beyond the maximum that could be expected from theory or probability. To state the case in its simplest terms, all that could have been predicted was: (1) that the removal of the moisture from the blaet would result in the saving of the heat required for its decomposition, representing from 3 to 5 per cent. of the heat-value of the coke used; hence about that quantity of fuel might be saved; (2) that the furnace would be somewhat more independent of variations in the weather; (3) that the campaign would be a little hotter; and (4) that the speed of the blowing-eugines would be decreased, at least in amount proportionate to the reduction in temperature of the air led to them. I do not think anyone anticipated a much larger output per day. The results actually attained were: (1) the furnace made an increase of 24.86 per cent. in the output of pig-iron per day; (2) it consumed 19.6 per cent. less coke per ton of pig-iron made; (3) the blowing-engines were run 15.8 per cent. slower; and (4) the saving in power made up for the power required to run the refrigerating-plant. In addition, the blast was hotter; the waste-gases cooler, because of their smaller volume; and there was a greater proportion of carbon dioxide to carbon

Jan 1, 1906

By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By M. M. Neale

The pottery department has been aptly described as the "heart of the zinc plant," md every operator of a horizontal-retort plant is acquainted with the fact that good retort practice is the keystone of the smelting process. Since retorts and condensers are clay products, it is obvious that improvements in other branches of the ceramic industry should be observed for possible adoption in the pottery process for zinc smelting. Deaeration of clay bodies is one of the improvements that have become fully, established in many brick and pottery plants. Our investigation of a number of these installations always yielded the same answer—improved practice. Improvement in workability, elimination of laminations, less porosity, greater wet and dry strength, were among the claims put forth for this process. All of these features are exceedingly desirable characteristics in the manufacture of a zinc retort. A preliminary test, which involved truck transportation of deaired slugs over a relatively long distance, did show the value of many of these characteristics in forming the retort. Results from the standpoint of , longer retort life in the smelting furnace were not outstanding. The idea lay dormant for several years but was revived again in 1940, when it was decided to make whatever changes were necessary in the equipment for pottery manufacture to fully demonstrate the process. A number of the manu- facturers of machinery for clay work were asked to submit proposals, and the plan finally adopted was extremely simple and economical. Machine FOR DeaeRRATING Selection of the ''Straight-line'' principle for conversion of the "Wettengel" pug mill to a ''vacuum-extrusion" machine preserved some usable parts of the original equipment, such as the drive mechanism, and main shaft. The converted machine consists of a feed hopper, a compression and shredding zone, a vacuum chamber, and an extrusion barrel, as shown in Fig. I. In operation the clay mix travels from the feed hopper into the compression zone, where it is compressed and finally forced around the tapered cone into the vacuum chamber. As it enters this chamber the clay body is shredded into thin plates, for exFosure to the vacuum. The shredder consists of a hub mounted on the main shaft, to which are bolted segmental sections, each of which carries shredder knives. The compression zone and extrusion barrel function as seals for the vacuum chamber and the shredded clay mix is agitated thoroughly during its exposure to the vacuum. A vacuum pump, equipped with a 3-hp. motor, is attached to this chamber, and maintains 25 to 26 in. vacuum during operation of the mill. Changes in Practice Prior to the adoption of the deaeration process, our standard pottery practice called for double mixing in the combination 7

Jan 1, 1944

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

By M. J. Sinnott

WITH the advent of nodular iron as an engineering material, considerable interest has been shown in developing this material for various applications. Generally the strength, hardness, or ductility are the more common properties used for design purposes but occasionally applications involving a knowledge of the thermal conductivity of the material is required. A search of the literature showed, rather surprisingly, that relatively little work has been done on this property for all types of cast iron. Insufficient data are available on thermal and electrical conductivities to develop the Weidemann-Franz ratio, or the Lorentz relationship, for estimation purposes. There are no data on nodular irons and the published data on malleable irons are quite sketchy. For these reasons the conductivity of the group of nodular irons listed in Table I were measured. Irons I to IV were made in such a fashion as to maintain the carbon and alloy content essentially the same while varying the silicon content. Test specimens were cut from the mid-section of 4-in. keel castings. Iron V is a commercial casting of nodular iron. The test specimen of this iron was cut from the center of a large cast billet 3x10x26 in. All alloys were tested in the as-cast condition. A microstructural examination showed that each iron had spheroidal graphite but the size and distribution varied with the silicon content of the iron. The spheroid size decreased while the number of graphite nodules increased as the silicon content of the iron was increased. The matrix structures of each iron consisted of pearlite and ferrite with the proportions varying from predominantly pearlite in the low-silicon iron to mostly ferrite in the high-silicon iron. The commercial heat, iron V, was predominantly pearlite probably because of its higher manganese and phosphorus content. Two methods for measuring the thermal conductivity were used. The first was a modification of the techniques described by Powell and Hickman and Van Dusen and Shelton,² the second method was a simpler technique described by Jakob and Hawkins." Since the agreement of both methods as tested on two sets of duplicate samples was excellent, the simpler experimental technique was used. The results of the measurements are given in Table II along with a summary of the microstructural constituents. These conductivity data indicate that as the percentage of silicon increases there is a corresponding decrease in the thermal conductivity even though the structure is changing from pearlitic to ferritic. Such a change in microstructure is usually accompanied by an increase in conductivity. A third factor involved in the behavior of these irons is the size and distribution of the graphite nodules. The relative amounts of graphite do not change greatly but the size and distribution do. Generally graphite improves the conductivity but in the present case such an effect is probably masked by the alloying effect from the silicon and its dispersion through the matrix. The thermal conductivity of the nodular irons studied is less than that of regular foundry irons by some 10 to 30 pct and is less than that of regular malleable irons.' The cause of the decreased conductivity is probably the more highly alloyed fer-rites obtained in these irons and the changed mode of distribution of the graphite as compared to the regular foundry irons. References R. W. Powell and M. J. Hickman: Journal Iron and Steel Inst. (1946) 154, No. 2, p. 99. 'M. S. Van Dusen and S. M. Shelton: U. S. Bur. Standards Journal of Research, RP668 (1934) 12, p. 429. ³M. Jakob and G. A. Hawkins: Elements of Heat Transfer and Insulation. 2nd Ed. (1950) New York. John Wiley and Sons. ' J. W. Donaldson: Journal Iron and Steel Inst. (1933) 128, No. 2, p. 255.

Jan 1, 1954

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By I. R. Kramer, L. J. Demer

Aluminum single crystals were pulled in an electrolytic cell allowing surface removal during the deformation. The extent of Stages I and 11 of the stress-st-aitz curve was increased and the slope decreased as the rate of metal removed from the surface was increased. An increase of the strain rate caused a decrease in the effectiveness of the metal removal. The data indicate that the work-hardening coefficient in Stage I is determined primarily by the conditions which exist on the surface of the crystal. In Stages 11 and 111, both surface effects and internal barriers are important. ALTHOUGH numerous investigations have been conducted on the plastic flow characteristics of metals in an attempt to explain the mechanism of work-hardening, relatively few studies have taken into account the influence of the surface. In all current theories of work-hardening it is assumed that the impediments to the movement of dislocations are within the crystal. The barriers due to the surface and the existence of solid and liquid films have been neglected even though it has been demonstrated that the surface exerts a large effect. A number of investigators1-l8 have shown that solid films on the surface of single crystals markedly affect their mechanical behavior. In general, the presence of a solid film tends to increase the yield stress and increase the work-hardening rate. Often, on single crystals, Stage I and, at times, Stage II regions are completely suppressed. Various mechanisms have been offered for the effects of oxide and metal films as well as the influence of electrolytes. Of these, concepts concerned with the locking of surface dislocation sources and the blocking of dislocations at the surface resulting in pileups appear to be actively considered at present. Barrett,11 Takamura,6 Gilman,19 Lipsett and King,20 Shapiro and Read,10 and Weiner and Gensamer21 are among those who have interpreted their results in terms of piled-up dislocations at the surface, while Adams.22 and Chalmers and Davis23 have explained their experimental observations in terms of locking of surface dislocation sources. In general, the change in plastic flow properties due to electrolytes has been explained in terms of the unblocking or unlocking of dislocations by the removal of the oxide films. In considering the two proposed mechanisms, it appears that the locking of sources of surface dislocations by a solid film should exert a primary influence only on the critical resolved shear stress for flow and not on the slopes of Stages I and 11. However, the blocking at the surface of dislocations from internal sources may also affect the critical resolved stress and furthermore exert an influence throughout the whole plastic range. In certain cases it does not seem feasible to explain the results of experimental observations in terms of locking of surface dislocation sources. The abnormal aftereffects found by Barrettll,12 by removing the oxide by an acid treatment are excellent evidence of the blocking of dislocations at the surface. Additional evidence in favor of a blocking due to a pileup of dislocations at the surface may be found from the observations that the critical resolved shear strength continues to increase with the thickness of the oxide layer until very heavy oxide layers are formed. If the locking of surface dislocations sources were the dominant factor, the critical resolved shear stress would not be expected to increase after all of the surface sources were locked by the formation of the oxide. This may be expected to happen after a few atomic layers of the oxide are formed. In spite of the above evidence on the strong influence of the surface on the plastic flow characteristic, this has been ignored in current theories of work-hardening. Seeger24,25 suggested that most of the dislocations may slip out of the crystal only when the specimen axis is within certain areas of the orientation triangle. In other areas the resolved shear stress in other glide systems is large enough to generate dislocations which can form Lomer-Cottrell locks, thereby decreasing the average slip distance in some directions and causing a larger hardening rate. Friede126 assumed that at the beginning of Stage 11, a large number of Lomer-Cottrell dislocations are formed by a catastrophic process which used up all the Frank-Read sources on the secondary slip-planes. In this manner a fixed number of Lomer-Cottrell locks is formed which act as barriers against which the dislocations can pile up. In Stage 111, Seeger24 and Diehl, Mader, and Seeger25 proposed that Lomer-Cottrell barriers are circumvented by the cross slip of extended screw dislocations. Cottrell and Stokes,27 Friedel,26 Cottrell,26 and stroh29 suggest that the Lomer-Cottrell dislocations collapse under the stress field of the dislocation pileup. It is the purpose of this paper to report the changes in Stages I, II,and III of the deformation process in

Jan 1, 1962

By Basil B. Zavoico

PRODUCTION of crude it in the United States during 1939 totaled about 1.255,776,000 barrels, an average of 3,440,482 barrels per day, 3.41 per cent above the 1938 output of 1,214,355,000 barrels but 1.83 per cent below the record pro¬duction of 1,279,160,000 barrels, in 1937. However only the two-week shutdown of oil fields in the Southwestern States in August and September prevented the domestic crude production from establishing an all-time record in 1939. Demand for all petroleum products for the first ten months of 1939 showed an increase of 7.04 per cent over the similar period of 1938. Domestic demand for all petroleum products was particularly benefited by the increasing industrial activity, advancing 8.37 per cent above the like period of the preceding year equivalent to a volume increment of 256,810 barrels per day; with motor-fuel demand gaining 5.83 per cent and demand for all fuel oils gaining 12.15 per cent over the corresponding period of 1938. The export demand for the first ten months of 1939 was slightly below the export movements during the same period of 1938, declining 0.56 per cent. The European war was a major factor in 1939 for the petroleum industry in the United States, even if, at the end of the year, the war had not yet resulted in the expected large shipments to England and France.

Jan 1, 1940

By H. H. Moss

OXYACETYLENE .cutting has experienced rapid development in the last few years and greater advances and expansion and broader application may be expected in the immediate future. Marked changes in cutting practice may be expected as a result of the advances in metallurgical science that have produced special alloy steels with properties requiring different cutting techniques than for ordinary low-carbon steels. Much current attention is being directed to those problems of modified cutting practices. Cutting has thus ceased to be merely a shaping problem. It is rapidly coming to have a predominantly metallurgical aspect. The problem is no longer how to cut a given shape, but how to cut a given steel. The answer

Jan 1, 1936

By RAYMOND M. LARSEN

The area covered by this paper is the same as that covered in 1944. Colorado, Montana, Utah, and Wyoming are included in the discussion and statistics, and brief mention is made of activities in the adjoining states, except Nebraska and New Mexico, which are considered separately (see pp. 187-189). The other adjoining states, North and South Dakota, Arizona, Nevada, and Idaho, have had virtually no oil or gas production, except in the gas field of Cedar Creek. Montana, which extends into North Dakota; the Pierre field in South Dakota, where gas is produced and separated in gas-water wells, and the abandoned Payette area in western Idaho. Seven gas wells were drilled in North Dakota, but no wildcatting was reported. Several unsuccessful wildcats were drilled in South Dakota, and some were continuing at the end of the year. Activity in Idaho and Nevada was negligible.

Jan 1, 1946

By F. Habashi

Conclusive evidence is given showing that the dissolution of gold in cyanide solution follows mainly the over-all equation A similar equation can also be written for the dissolution of silver. Theoretical derivation of the velocity equation for this reaction has been obtained, which describes quantitatively the experimental facts. The equation is as follows: where [CN-] and [O2] = the concentrations (in moles/ml) of cyanide and dissolved oxygen, respectively. DcN- and Do2 = the diffusion coefficients of cyanide and dissolved oxygen; 1.83 x 10-5 and 2.76 x 10-5 cm2 sec-1, respectively. A = the surface area of the metal in contact with the aqueous phase, in cm S = the thickness of the boundary layer; varies between 2 and 9 x 10-3 cm, depending on the speed and method of agitation. Rate being expressed in g. equiv. sec-1. INTRODUCTION During recent years a number of papers have been published on the kinetics of dissolution of gold and silver in cyanide solution.1,6 The authors agree that the rate of dissolution is diffusion-controlled, but disagree regarding the mechanism of the reaction. Some authors'-3 support the Bodlander equations: The apparently conflicting results, when critically reviewed, are concordant and lead to the conclusion that the proper equation for the dissolution reaction should be only Eq. 1. This conclusion is based on the following facts: 1) For every 2.2 equivalents of metal dissolved one mole O2 was consumed. 2) For every 1 equivalent of metal dissolved, 2 moles of cyanide were consumed.' 3) Hydrogen peroxide is formed during the dissolution of gold or silver, and for every 2.2 equivalents of metal dissolved, one mole H2O2 was produced.1,2 The fact that Kudryk and Kellogg4 did not detect H2O2 during the dissolution of gold should not throw doubt on the many affirmative reports of other investigators. Lund2 has shown that depending on the crystalline nature of the silver surface, (e.g. method of etching the sample) H2O2 may undergo catalytic decomposition heterogeneously according to: Further Kudryk and Kellogg4 carried out their experiments in the presence of 0.5% KC1 to achieve a greater electrolytic conductivity, and Matsudaira7 has shown that H2O2 is catalytically decomposed (homogeneously) in the presence of C1- ion in alkaline solution. 4) Experiments carried out by Boonstra8 and Lund2 showed that the dissolution of gold and silver respectively in KCN + H2O2 in the absence of oxygen was a slow process. Thus the reaction takes place to a minor extent only. Further kinetic studies showed that: 1) The rate of dissolution depends on the surface area of the metal in contact with the liquid phase, thus indicating that the process of dissolution is a heterogeneous process. 2) The rate of dissolution depends on the speed of stirring,5,6 thus indicating that the process is controlled by a physical phenomenon.

Jan 1, 1967

By Herty, C. H.

No attempt will be made here to review the previous work done by investigators on the general subject of inclusions, because it was discussed sufficiently in an early cooperative bulletin of this series (No. 36, 1928), and reference was then made to general bibliographies. The work described in this present bulletin deals directly with the study of the mechanism of deoxidation of steel with aluminum and the formation of inclusions containing alumina. Unquestion- ably, such inclusions are encountered in most steel-making practices and little has been done to determine their characteristics. Aluminum is used to ensure rapid deoxidation during the solidification stages of the steel. For this reason the possibilities of inclusion elimination are slight and alumina-containing particles will undoubtedly be present in the ingot. Besides this common practice, aluminum is often used in the ladle with other deoxidizing agents such as silicon and manganese. Ladle additions of aluminum are made to rimming steels to obtain the correct partial deoxidation desired in this type of steel. In killed steels the aluminum is added to ensure soundness, as far as blowholes are concerned, in the ingot. In either rimmed or killed steels, alumina or alumina-containing inclusions are found therein, the amount and type depending on the oxidation of the metal, the amount of aluminum added, and the addition of other deoxidizers.

Jan 1, 1957