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The world's production of petroleum in 1926 amounted to nearly 150 million long tons, of which India contributed 0.72 per cent. In 1927, this figure jumped to some 172 million long tons, of which the Indian proportion, on a practically stationary production, fell to 0.64 per cent. In 1928, there was another substantial rise in the world's production, which reached the figure of over 181 million tons. In 1929, there was another jump to over 202 million tons, but in 1930 the world's production fell to about 193% million tons, in 1931 to about 187 million tons, and in 1932 to about 183 million tons, while in 1933 the production rose again to about 202 million tons, in 1934 to about 215 million tons, and in 1935 to 233 million tons1. Decreases were shown by Poland, Sarawak, Egypt, Rumania and France. All other important producers showed an increase in production, by far the largest being due to Iraq, as a result of the opening of the pipe line to the Mediterranean. The United States contributed 60.9 per cent of the world's supply in 1935, Russia 10.7 per cent, Venezuela 9.4 per cent, Rumania 3.9 per cent and Iran 3.1 per cent. In 1928, India contributed 0.64 per cent, which fell to 0.60 per cent in 1929 and rose to 0.62 per cent in 1930, 0.63 per cent in 1931, and 0.64 per cent in 1932, and fell again to 0.62 per cent in 1933, to 0.60 per cent in 1934 and to 0.50 per cent in 1935; her position on the list of petroleum-producing countries fell from eleventh in 1929 to twelfth in 1930 to 1933, her place being taken by Trinidad and to thirteenth in 1934 and 1935, owing to the production by Iraq. The production of petroleum in India (including Burma2) increased slightly from 322,025,280 gal.3 in 1934 to 322,662,336 gal. in 1935, the highest figure in the history of the industry. The increase in 1935 is due to an increase of some 4 million gallons in Assam, almost offset by a decrease of 31/2 million gallons in Burma. This increase in output in 1935 was accompanied by an increase in estimated value amounting to Rs. 22,73,550 (£170,944).

Jan 1, 1937

By J. P. Newell, R. W. Storey

AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery .augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120 This head design proved to be very satis-

Jan 1, 1952

By V. I. Purcell, S. C. Sun. R. E. Snow

A study including effects of 7) pH value, 2) fatty acid collector, 3) fuel oil, 4) interfering ion, 5) particle size, and 6) operational variables. Test results indicate feasibility of fatty acid flotation under certain restrictive conditions. FATTY acids have been used as standard collectors for floating the matrix1-8 but not the leached zone phosphate ores. After a series of investigations, Davenport9 and Tarbutton10 concluded that the Florida leached zone ores tested were unamenable to fatty acid flotation and must be upgraded by floating the siliceous gangue with Armac-T as collector. The cationic flotation was estimated11 to cost almost ten times as much as a fatty acid process that would ideally give the same flotation grades and recoveries of phosphates. Mineralization: Extensive deposits of leached zone aluminiferous phosphate occur in Florida."= The ore sample used for this work was obtained from the Virginia-Carolina Chemical Corp., Clear Springs area, Florida. The ore is a potential source of uranium and aluminum as well as phosphorus. Since the uranium and the recoverable aluminum are contained in some of the phosphate minerals, an upgrading of phosphate results in a corresponding enrichment of both uranium and aluminum. The phosphate minerals in the ore are primarily pseudo-wavellite, millisite, and carbonate fluorapatite, with a minor amount of wavellite. Quartz and clay are the common gangue minerals, quartz being predominant. Others present in small amounts are ilmenite, hydrated iron oxides, staurolite, monazite, and zircon. Experimental Procedures: After being dried to less than 1 pct surface moisture the material was dry-ground in a Hardinge conical ball mill to —6 mesh. The ground product was classified into 6/20, 20/200, and —200 mesh size fractions. On the basis of Table I, the coarse and fine size fractions were considered as phosphate concentrates, because of their high phosphorus contents. In contrast, the 20/200 mesh fraction, which was low in phosphorus, was used as the flotation feed. All the flotation tests, unless otherwise stated, were performed in a laboratory Fagergren machine under the following conditions: 1) 400 g of solid feed for each test, 2) 2000 rpm impeller speed, 3) 8.9 pH and 4-min conditioning, and 4) 3-min flotation. The procedure used for the quantitative bubble pick-up tests has been described previously.18

Jan 1, 1958

By Claude H. P. Lupis, John F. Elliott

WAGNERL described the thermodynamic behavior of a metallic solution consisting of the solute components 2, 3,... at very dilute concentrations in the solvent, 1, in terms of the excess partial molar free energy, or alternatively the logarithm of the activity coefficient. In the Taylor expansion of FiE, by neglecting the second- and higher-order differential terms, he obtained the excess partial molar free energy as a linear function of the composition:

Jan 1, 1965

By H. W. Bell

There was considerable prospecting for new supplies of oil in Arkansas during the past year, regardless of the overproduction affecting the industry throughout the country. Justification for this new work was not lacking, as the local markets more than threatened to absorb a declining production. There were, however, no important new discoveries in the state during 1929. The McDonald area in sec. 2515, S.-18 W., threatened to expand into a major producing area. Oil showings had been encountered here in wells drilled by the McDonald Oil Corpn. as early as the fall of 1928. In July, 1929, an initial production of 1000 bbl. of 32" oil was obtained in McDonald Bros. B-3 Wilson, from a sand at 2780 to 2786 ft., which is about 80 ft. higher than the sand previously tested in the neighboring wells. This production declined rapidly. At the end of the year there were six producers making about 200 bbl. per day total. Seven dry holes have temporarily stopped development in that area. The showing of B-3 was sufficient to cause considerable leasing activity. The area lies several miles west of the Louann portion of the Smackover field. The discovery well went to 2873 ft. and found Glen Rose lime in bottom. The age of the producing sand is in doubt; it seems closely related to the Tokio sand. During 1929, several paying wells were brought in, as a northeastern extension to the Smackover Heavy area, in sec. 34 and 35-15-15, from the Nacatoch sand. Over 20 new wells were drilled and resulted in at least 1500 bbl. production. The down-dip or off-structure territory contiguous to the Smackover uplift was further tested at various locations with the usual results; that is, a showing of "salt water gas," which soon blew off and in some cases a slight showing of oil. These gas showings, found further down the dip than oil, are the results of the ability of water to take gas into solution at the rate of about 3 per cent. by volume at atmospheric pressure and proportionally larger quantities, if available, at higher pressures (measured on the absolute scale). During the year no off-structure wrinkles sufficient to trap conlmercial quantities of oil have been found outside of the other known fields of

Jan 1, 1930

By G. Sandoz, C. A. Siebert

OIL quenching of steel, in good commercial practice, is carried out using a great deal of agitation in the quenching bath. Many of the tests reported in the literature represent the results obtained on steels quenched into still oil. Scott1 describes three stages of cooling in liquid quenching baths, namely: "State `A'-Vapor Blanket Cooling-In this, the first stage, a thin stable vapor film surrounds the hot metal. Cooling is by conduction and radiation through the gaseous film and is therefore relatively slow. "Stage `B'-Vapor Transport Cooling- Termination of the `A' stage is marked by wetting of the metal surface. Vapor forms copiously in bubbles and is carried away by gravity and convection currents to condense in cooler surrounding liquid. This is the fastest stage of cooling. "Stage `C'-Liquid Cooling--The `B' stage ends as the surface temperature of the metal approaches the boiling point of the quenching liquid. Vapor no longer forms, so cooling is by conduction and convection and the temperature difference is greatly decreased. This mode of cooling is slower than that of the `B' stage." Mechanical agitation of the quenching medium will accelerate all three stages of cooling. The greatest effect, however, will be noted on stage `B' because the removal of the bubbles from the surface of the steel will not be entirely dependent upon gravity and natural convection currents. The method employed in this investigation for evaluating the oils was the end quench test. The various oils were substituted for water as the quenching liquid and hardness determinations were made at various distances from the quenched end. Most of the tests were run using a 3/8-in. orifice with a 2 ½ -in. stream height. However, to check the effect of other velocities two additional conditions were used, namely: (I) A 3/8-in. orifice and 1-in. stream height, and (2) a ½ -in. orifice and a 3 ½ -in. stream height. In all cases the samples were suspended so that the quenched end was ½ -in. above the orifice. The steel used was an NE 9450 having the following analysis: [ ] Some tests were run on an NE 8740, 3312, and a 4340 steel. The results obtained on these steels confirmed those obtained on the NE 9450 and have therefore been omitted' from this paper. The test bars were machined from 1 1/8 -in. stock to 1-in. diam by 4 in. long.

Jan 1, 1948

By R. W. Bartlett

Hydrometallurgical processes for copper flotation concentrates avoid the SO2 emission problems associated with smelting, but they require oxidation of copper to obtain solubilization during leaching. The resulting copper ions must be reduced to metal, which normally requires large amounts of energy or energy equivalent reagents such as hydrogen or iron. The conventional reduction method is electrowinning which is labor intensive and involves 35 to 40% of both the entire operating and capital cost of the better hydrometallurgical processes. There is considerable incentive to reduce the cost and energy required for producing copper ions from solution. Furthermore, it is thermodynamically possible to do this using sulfur contained in the concentrate itself. In fact, the thermodynamic potential of oxidizing sulfur from S+4 to the S+6 state is greater than required to reduce cupric ion to metallic copper.1 Realization of this potential in a practical process would significantly reduce the cost of hydrometallurgical processing of sulfide concentrates because sulfur would become a cost-free reducing agent. An apparently practical method is to use SO: and HSO3 ions, obtained by ammonia scrubbing of SO2 from a concentrate roaster gas, to reduce leached copper to metal in an autoclave. This reduction step is the Jumau 1907 A series of steps, including sulfite reduction, constituting a crude flowsheet was suggested by Parker in 1976.3 The present paper describes a detailed complete. sulfite process flowsheet based on materials and energy balances, discusses the chemistry, and discusses further work that is required to develop this process. Process materials, utilities costs, and energy requirements are projected to be unusually low because of the utilization of sulfur from the concentrate. Process Description The sulfite reduction process requires a copper concentrate containing approximately as much sulfur on a weight basis as copper. For those few concentrates that are deficient in sulfur, additional sulfur can generally be obtained by allowing more pyrite to float in the concentration process. The process steps, shown in [Fig. 1], are (1) a fluid bed roast of the concentrate, (2) a leach of the roaster calcine using recycled barren liquor from the reduction autoclave, (3) scrubbing of the SO2 gas with ammonium sulfite liquor to produce ammonium bisulfite, (4) reduction and precipitation of copper in an autoclave by combining part of the SO2 scrubber effluent (SO5

Jan 1, 1980

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

[NUMERICAL CODE TO MAPS (Region Listed in Roman Numerals after Each Petroleum Section) 1 Alaska 2 Arizona 3 Black Hills 4 Boston 5 Carlsbad Potash 6 Central Appalachia 7 Chicago 8 Cleveland 9 Colorado 10 Columbia 11 Connecticut 12 Delta (VIII) 13 Detroit 14 East Texas (VI) 15 El Paso 16 Gulf Coast (VII) 17 Kansas (IX) 18 Lehigh Volley 19 Mid-Continent (IX) 20 Minnesota 21 Montana 22 Nevada 23 New York]

Jan 1, 1961

By Edward H. Robie

SHOULD the name of our Institute be changed? Perhaps one should say, should it again be changed, for until 1919 the name was the American Institute of Mining Engineers. When the American Institute of Metals joined our ranks we became the American Institute of Mining and Metallurgical Engineers. To make it a full mouthful, and strictly legal, one should add the word "Incorporated." At the June meeting of the Board of Directors it was suggested that this name was not a particularly happy one, especially so far as members of the Petroleum Branch, comprising a quarter of our membership, were concerned-not particularly appropriate as the name for the professional society for petroleum engineers. Apart from the petroleum group, the present name is felt by some not to be sufficiently comprehensive. Most geologists and many metallurgists, ceramists, and fuel technologists, for instance, are not engineers. They could never qualify as registered professional engineers under the licensing laws and yet they are valued and fully qualified Members of the AIME. The Directors, at the June meeting, thought the idea of a change in name should be presented to the membership for discussion, and suggested this column as the avenue of approach. Nine years ago Dean Steidle, of Penn State, recommended among other things that the name of the Institute be changed to "American Institute of Mineral Technologists and Engineers." In an editorial in Mining and Metallurgy in January 1944 objection was offered to this name but "American Institute of Mineral Engineers" was suggested. A special committee appointed by the Board to review Dean Steidle's suggestions (W. B. Heroy was Chairman) suggested that if the AIME were starting from scratch, the American Institute of Mineral Engineers might be a preferred name. It was not thought that the change suggested by Dean Steidle was one of major importance, and the comment was made that "the present name has gained prestige through many years and is cherished by our membership. An important element of 'good will' is attached to it and some of this would be unquestionably sacrificed by any change." In M&M for February 1945, Oliver C. Ralston went into the derivation of the terms mineralogy and metallurgy, and pointed out that both Mining and Metallurgical mean "digging," etymologically. He went on to show, with tongue in cheek, that if we want a short and all-inclusive name it should be American Institute of Geo-urgists, or, for euphony, Geolurgists. Oliver's brilliant development seems to have been received with speechless wonder! Should a decision ever be made to change the name, we think most members will agree that the American Institute of Mineral Engineers is to be preferred over anything yet suggested. "Mineral" has become, through usage, a much broader term than is indicated in the dictionary. Webster states that a mineral, in the true sense, must be inorganic, but Murray's Oxford English Dictionary seems more liberal, defining "mineral" as "any substance which is obtained by mining; a product of the bowels of the earth;" and "mineral oil" as any oil of mineral origin, as petroleum or shale oil. Certainly "the mineral industry" is ordinarily taken to include those activities based upon processing all the metallic and nonmetallic ores and deposits found in the ground, including the fuels. One advantage of this title is that the familiar abbreviation, "AIME" need not be changed. The advisability of maintaining a well-known abbreviation is evident, and was recognized, for instance, when the Committee for Industrial Organization became the Congress of Industrial Organizations some years ago. But if the petroleum engineers are the ones to be chiefly considered in revising the name of the Institute, it is by no means certain that they would feel that they are much more adequately recognized in a group of Mineral Engineers than in a society of Mining and Metallurgical Engineers. 'And then there remain, of course, the considerable number of professional members of the Institute who are not engineers at all. Comment from readers is invited.

Jan 1, 1952

By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2. that galena freed of surface oxidation products and lead carbonate ("clean" galena) is water-repellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. of 1.18 sp. gr. hydro chloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (I) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler's reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table I.

Jan 1, 1941

The following is a report of the papers submitted to the Papers 'and Publications Committee during 1928: The Committee held nine regular meetings during the year 1928. During that period there were presented to the Institute 214 papers which were acted upon as follows: Accepted as Technical Pub1ications............................ 85 Declined for publication...................................... 16 Action pending, Dec. 31...................................... 25 Manuscripts held for annual volumes, Dec. 31................... 7 Withdrawn temporarily...................................... 1 Accepted as Preprints........................................ 20 Printed for first time in volumes.............................. 35 Published in Mining and Metallurgy........................ 12 Papers in Technical Publication No. 156 (Coal Classification) and not accounted for elsewhere in this table..................... 10 Mimeographed only*................................... 3 Total.................................................. 214 * A considerable number of papers were mimeographed for the annual meeting. Of the 85 papers accepted as Technical Publications 8 were reprinted in the Transactions, 7 in Proceedings of the Institute of Metals Division (1928), 7 in Iron and Steel Technology in 1928, 13 in Geophysical Prospecting, and 50 were in Technical Publication form on Dec. 31. Of the 20 papers accepted as Preprints 1 was reprinted in the Transactions, 13 in Petroleum Development and Technology in 1927, 2 in Geophysical Prospecting, and 4 were in Preprint form on Dec. 31. Of the 35 papers printed for the first time in the various volumes 8 were included in the Transactions, 2 in Proceedings of the Institute of Metals Division (1928), 1 in Iron and Steel Technology in 1928, and 24 in Petroleum Development and Technology in 1927. Of the 12 papers accepted for Mining and Metallurgy 1 was, accepted for Geophysical Prospecting and 1 for the Transactions. There were published in 1928 113 Technical Publications containing a total of 1928 pages, as against 88 in 1927, totaling 1528 pages. The Technical Publications published in 1928 were classified as follows: Group A, Metal Mining, 17 papers (361 pages); B, Milling and Concentration, 4 papers (39 pages); C, Iron and Steel, 15 papers (256 pages); D, Non-ferrous Metallurgy, 13 papers (191 pages); E, Institute of Metals, 36 papers (588 pages); F, Coal and Coke, 15 papers (392 pages); G, Petroleum and Gas, 10 papers (246 pages); H, Non-metallic Minerals, 3 papers (33 pages); I, Mining Geology, 18 papers (356 pages); K, Mining Administration, etc., 3 papers (47 pages); L, Geophysical Prospecting, 21 papers (430 pages).

Jan 1, 1929

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

Jan 1, 1931

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By M. C. Flemings, T. S. Piwonka

Pore formation is examined analytically in cellu-larly solidified single crystals, in cylindrical castings of pure metals and alloys, and in unidirectionally solidified castings. Effects are considered of fluid flow. dissolved gas, and surface tension. Experimental results show that flow through a partially solid "mushy" aluminum alloy obeys relations similar to those applicable for flow through other types of porous beds. Flow rate is proportional to the square of the fraction liquid (fL) for fL less than 0.3. Results indicate models chosen for mathematical description of pore formation in alloy solidification are valid. ONE of the solidification variables which is influential in determining mechanical properties of castings and of wrought material produced from cast ingots is porosity. This porosity may result from shrinkage, dissolved gases, or a combination of both, and may take the form of either macroscopic pores in localized areas of the casting or microporosity evenly distributed throughout large areas of the casting. In alloys which freeze over a range of temperatures some microporosity is generally found after solidification. There has been much discussion as to whether the micropores are caused primarily by shrinkage, by gas, or by a combination of both.&apos;-3 There has, however, been little experimental or analytical work performed to delineate the relative contributions of shrinkage and gas in causing microporosity or to quantitatively describe the influence of processing variables on microporosity. Porosity other than microporosity (e.g., center line shrinkage) has also received only limited quantitative treatment.495 The aim of this work is to examine analytically the general problem of pore formation in solidification and to perform limited confirmatory experiments. Consideration is first given to shrinkage porosity in pure and nearly pure metals (shrinkage in cellular growth, centerline shrinkage in cylinders). Next, a discussion is given of formation of shrinkage-caused microporosity in unidirectional solidification and in "mushy" solidification. Finally, influences of dissolved gas and surface tension on microporosity are examined. Numerical results are given for aluminum and an aluminum alloy. Typical examples of microporosity are shown in Figs. 1 to 3, for 1) cellularly solidified aluminum, 2) sand-cast aluminum alloy, and 3) low alloy steel. SHRINKAGE POROSITY IN PURE AND NEARLY PURE METALS 1) Cellular Growth. In cellular freezing of an impure liquid, liquid grooves may exist over a considerable length of the growing crystal.6 The cross-sectional area of the grooves decreases with increasing distance from the cell tips; the root of the groove is blunt if the liquid at this point reaches eutectic composition. As a result of volume contraction during solidification, flow occurs down the groove, parallel to the growth direction; hence, there must be a pressure drop from the groove entrance to points within the groove. The geometry of the groove is simplified to that of a circular cylinder of radius r and length L, Fig. 4, L » r, and a simple and useful limiting case is obtained. This is that, in the circular cylinder freezing at constant velocity, the pressure at the root of the groove is lower than that pressure at radius r in grooves of other geometries where r decreases continuously to a lower limit at L. As discussed below, a pore resulting from a given pressure difference

Jan 1, 1967

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Ti-Mn alloys were studied in order to determine the factors affecting the mechanical properties of &stabilized titanium alloys. The principal compositional factors have been found to be solid-solution strengthening, the martensitic transformation, and instability of the P phase. Structural factors, such as grain size and shape, were found to have more influence on ductility and toughness than on strength. THE alloys of titanium with the &stabilizing elements offer the chief hope for developing useful heat treatments. Conversely, the heat-treatment response possible with the p-stabilizing elements causes difficulties such as weld embrittlement and thermal instability during service at elevated temperature. Therefore, it is of considerable technical importance to understand the factors that govern the heat-treatment responses in these alloys, so as to be able to soften the alloys if they are embrittled by an adventitious heat treatment, to render them stable in service, or to harden them while maintaining adequate ductility and toughness. The Ti-Mn system is a good example with which to demonstrate the factors that govern strength and heat-treatment response in. a P-stabilized system. The region of the a-j3 transformation, after the work of Maykuth, Ogden, and Jaffee,&apos; is shown in Fig. 1. The a solubilities are low. This means that, in the two-phase a-p field, partition of manganese between the two phases occurs practically only to the P phase. The solid-solution effects are therefore chiefly the result of solution in the ,8 phase. The eutectoid occurs at 20 pct Mn and 550°C, and proceeds very sluggishly. It can be ignored in heat treatments in hypo-eutectoid alloys, except for long-time storage at low temperatures below the eutectoid temperature. Even here, there is some question that diffusion proceeds far enough to involve eutectoid decomposition. Three compositional factors bear on the mechanical properties and structure of titanium a-P alloys. These are: 1—solid-solution strengthening, 2—mar-tensite transformation, and 3—P instability. Combined with the purely structural factors of grain size and shape, these govern the properties of the alloys. Perhaps the most important factor is solid-solution strengthening. The facts that manganese dissolves in a titanium to a maximum of only 0.5 pct and most of the manganese partitions to the p phase dominate the structure and properties of the a-/3 alloys. Because of the overwhelming preference of manganese for the ,3 phase, the P phase is harder and the a phase is softer. The relative amounts of both phases may be modified by heat treatment in the a-P field as application of the lever rule in the two-phase field clearly shows. A critical temperature in the Ti-Mn diagram is 800°C. This is the P transus temperature of the 6.4 pct Mn alloy, which has the lowest manganese content which will form all retained-P phase on quenching to room temperature. Any quench performed from below 800°C will produce a structure consisting of only a, a plus retained P, or retained p, for alloys of the compositions used in this work. For alloys containing less than 6.4 pct Mn, any quench from above 800°C will always result in structures

Jan 1, 1955

By R. B. Falk, F. E. Luborsky

Small iron particles in mercury pow by diffusion of iron atoms through the mercury. Iron particles, with diameters about 200Å, have been stopped from gvowing in size, even up to the boiling point of mercury, by the addition of a third metal. The metal additives were classified according to whether they produced 1) negligible inhibition, 2) some inhibition, or 3) marked inhibition of the growth rate. Metal additives which resulted in a marked inhibition of iron-particle growth form a stable monolayer on the iron particles. Only those metals which may form compounds with iron showed this pronounced effect. The one exception was manganese. Metal additives which resulted in no inhibition of growth, showed no evidence for adsorption and could not form compounds with iron. None of the added metals, even those which strongly inhibited particle gvowth and thus had adsorbed on the particle surface, actually formed any compounds with iron at room temperature at the concentrations required for complete inhibition of growth. ThE stabilization of the size and shape of metallic particles dispersed in liquid metals has important technological implications in "homogeneous" nuclear reactor systems and in elongated particle magnets and is directly related to the problem of corrosion by liquid metals. Growth in these par-ticulate systems may occur by diffusion of atoms from surfaces of high energy, corresponding to a small radius of curvature, to surfaces of low energy or large radius of curvature. Thus, small particles dissolve and large particles grow to increase the average diameter of the particles. reenwood&apos; has analyzed this diffusional growth of a system of particles containing a distribution of sizes and has obtained reasonable agreement with data on the growth of uranium particles in liquid sodium and UPb3 particles in liquid lead. Greenwood concluded from his analysis that the chief factors promoting stability of dispersed particles growing by a diffusion mechanism are large mean radius, high density, and low molecular weight with low values of the solute diffusion coefficient, the solubility, and the interfacial tension. In the case of elongated particle magnets the system of interest is that of iron particles dis- persed in mercury. Previous work,2 concerned with "spherical" particles in mercury, has indicated a diffusional growth mechanism similar to that discussed by Greenwood. It has also been shown3&apos;4 that the addition of certain metals to Fe-Hg dispersions results in the formation of a monatomic layer of adsorbed atoms on the iron particles. In this paper we will show that this adsorbed layer provides the decrease in the iron-atom flux through the mercury necessary for size stabilization. The general features of the stabilization of the iron particles in mercury through the formation of this "coating", with many different metals, will be described. EXPERIMENTAL RESULTS Iron particles in mercury were prepared by elec-trodeposition,2, 4 and measurements2, 4 of coercive force HCi) and saturation induction (Is) were used to follow changes in size and composition during thermal aging in the mercury in the presence of relatively small amounts of an added metal. In Fig. 1 is plotted the aging behavior of spherical particle samples in the presence of some of the added metals to be discussed. The iron particles have an initial average diameter of 180Å. Each sample was aged for 20 min at each temperature in succession in the presence of a twofold to threefold excess of added metal over that required to form a monolayer on the iron particles. These are the same samples used previously3 to study the adsorp-

Jan 1, 1965

By H. C. Chao, W. F. Hosford, L. H. Van Vlack

The negative "plastic Poisson&apos;s ratio" suggested in earlier studies of Mus deformation is analyzed, and the results are verified experimentally with NaCl crystals. In the early stages of deformation where the primary {110}(110) slip predominates, compression along. the [001] direction produces contraction along the lateral [011] direction plus a compensating expansion along. the [100] direction. With additional strain, the primary slip is supplemented by secondary {111}(110) slip so that the above contraction diminishes and a more typical deformation appears. THE shape change of bee and fee crystals deformed by compression or tension along [011] has been analyzed in some detail and shown to be responsible for the development of peculiar microstructures in [011] fiber textured polycrystals of these metals.1&apos;3 This paper concerns the unusual shape change accompanying [011] compression of NaCl crystals. It is the direct outgrowth of an earlier investigation of the deformation of manganese sulfide inclusions in steel.3,4 In that investigation, cylindrical specimens of steel containing small oriented crystals of MnS were prepared by powder metallurgy and plastically compressed. The flow of the inclusions was determined relative to that of the steel by sectioning the composite and measuring the length-to-width ratio L/W of the inclusion and diameter-to-height D/H ratio of the steel cylinder on the plane of section. These L/W ratios, normalized by dividing by the initial LO/WO ratio of the inclusion, were compared with the normalized D/H ratio of the steel cylinder. Of particular interest here are the deformation characteristics of an inclusion oriented with [Oil] parallel to the compression axis. When measurements were made on sections parallel to the (100) plane of the inclusion, the L/IV ratios were only slightly in excess of unity, indicating a high apparent hardness of the [011] criented inclusion. However, measurements on a (011) plane of section resulted in L/W ratios which were much larger, Fig. 1. These observations prompted an analysis of the strains resulting from slip in an MnS crystal compressed along [011.]. CRYSTALLOGRAPHIC ANALYSIS Manganese sulfide has the NaCl crystal structure, and the predominant slip system is {110}(110). A secondary system, {111}(110), has also been reported.= {110}(110) Slip. When a crystal is subject to a uni-axial compressive stress 011 along [011], four slip systems, (101)[101.], (101)[101.], (110)[i10], and (110) [ 110], will be equally stressed with a shear stress t = 0.2 011 while the other two {110}( 110) systems will be unstressed. The normal strain En along any reference axis n resulting from slip is given by Schmid&apos;s law: en = S COS ?in COS in ?i 111 where ?in and +in are the angles between n and the i slip direction and n and the i slip plane normal, respectively, and where ?i is the shear strain on the i slip system, For the four active slip systems above, the cos ?in cos +in terms are all equal when the reference axes are the [011] compressive axis, [011] and [ 100]. Eq. [I.] therefore reduces to en - cos ?n cos +ny [2] where y =S?i for all slip systems. Substituting the appropriate angles, Eon = 0.25? 110 eon - 0.25y110 [3] €100 = -0.50y 110 The interesting feature of Eqs. [3] is that they predict that the strains in the [011] and [011] directions, resulting from {110}(110) slip, are equal and of the same sign. Thus when a crystal is compressed along [011], it will contract along the lateral [oil] direction

Jan 1, 1967