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By John V. Beall

W hen the blasts went off on West 11th St., just off 5th Ave. in New York City, James Michaels, editor of Forbes magazine, was in his office a few doors away reviewing color layouts with his production manager. Having once been a reporter, he grabbed his trench coat and dashed for the street to be con- fronted by the demolished townhouse which had been turned into a bomb factory by youths. To Michaels, this shocking episode supplied the exclamation point to thoughts he was formulating that an era had ended and a new one was beginning in the economic and social climate of the U. S. "For twenty years corporate profits, the stock market, middle income pay have gone up and up. . . The illusions of twenty years are in confrontation today with changed needs," he said. "International omnipotence is economically beyond our means, . . The anti-pollution and community renewal people are not nuts in tennis shoes who will go away. . . That corporation presidents can report an increase in earnings every year is an illusion that will be dropped. . . There has been a $200 billion shrink in value of stocks and bonds since Nixon came into office" were some indicators Michaels mentioned.

Jan 1, 1970

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By Walter Lang

The year 1931 has shown a marked change over 1930 in New Mexico, with respect to the volume of activities attendant upon the petroleum industry. Although the total production of oil and gas this year exceeds that of preceding years, the results have been attained from established units operating under restriction, but capable of supplying far more than the economic conditions justify. The presidential order of March 12, 1929, that "there will be complete conservation of Government oil in this administration," has merely anticipated a normal consequence of overdevelopment. As a result of the combined economic and legal restrictions imposed, very little new drilling has occurred during the year. Even in proven areas the drilling of offsets has been curtailed to the absolute limit of requirements. Scouting and sample-cutting, which in 1930 were still in a state of feverish activity, are at low ebb, and lease buying has reached a condition of stagnation. A number of the major oil companies have either materially reduced their field and office forces or completely eliminated local office representation. Two tests of particular interest, because correlation shows them to be structurally high although they failed to produce, are the National Securities well drilled six miles west of the town of Hobbs, on sec. 33, T.18 S., R.37 E., Lea County, to a total depth of 4272 ft., which developed a flow of 4,000,000 cu. ft. of gas at 3860 ft., and a show of oil; and the Western Drilling Co. No. 1 State, sec. 16, T.20S., R.32 E., Lea County. The latter test found dead oil at 2575 to 2580 ft., and sulfur water at 2745 ft., increasing to 2780 ft., representing the zone from which production was generally expected. The well was drilled to 4013 feet. The discovery of sulfur at about 950 ft. in the deepening of an old water well (Pearson, NE. 1/4 sec. 8, T.16 S., R.25 E.) drilled in the Little Cottonwood area northwest of Artesia led the Union Sulphur Co. to drill three prospect tests on a block of acreage in the vicinity during the summer and fall. The results of the investigation have not been disclosed. The Kummbaca Oil and Gas Co. drilled the T. J. Kerline No. 1, in sec. 34, T.21 N., R.30 E., Harding County, gaging 3,654,000 cu. ft. of 98 per cent CO² at 940 ft. The Barton structure, 20 miles east of Albu-

Jan 1, 1932

By Russell G. Wayland

This paper gives the author&apos;s personal idea of the general viewpoint of the world&apos;s largest mica consumer, the U. S. Army, toward the supply, uses, and conservation of mica. However, to cover so broad a subject in a brief paper will require the dismissal of many phases with little or no mention. For example, it will be necessary to omit further reference to phlogopite or amber mica, even though amber block and splittings for certain spark plugs and commutator segments present some supply problems. This paper will deal entirely with muscovite, or white mica. Muscovite Mica Muscovite mica is available commercially in four general forms; namely, as block mica, as splittings, as washer punch, and as scrap mica.1 No strategic importance is attached to washer punch and scrap mica, even though scrap has found some use in military construction and in electrical ceramics. The use of washer punch as such has fallen off with the non-manufacture of household electrical appliances. Some qualities of block mica are also of little or no interest, but other qualities of block mica and all splittings are considered of vital importance. Army equipment requires large amounts of muscovite mica splittings in the form of built-up mica commutator segments and coil insulation in motors and generators. Other military items using significant amounts of muscovite splittings are transformers, switchboards, and blasting apparatus. Flexible mica tape, made from bookform or loose-dusted splittings cemented to paper, linen, glass cloth, and other backing, is widely used in coil insulation in heavy electrical equipment and in aircraft generators. All muscovite mica splittings come from India, principally because of the enormous amount of hand labor required in their preparation. In this emergency, the need for them was anticipated and large industry and government stocks were on hand, while shipments have continued to come by sea in spite of wartime hazards. With the possible exception of certain bookform splittings, no trouble is anticipated in supply. Accordingly, the remainder of this paper is devoted to block (or sheet) muscovite mica, including condenser film that is split from block. The Mica Problem Block muscovite mica is commercially classified into the following general qualitie3, beginning with the best quality: 1. Clear and Slightly Stained (C & SS). 2. Fair stained (FS). 3. Good stained (GS). 4. stained (s). 5. Heavy Stained (HS). 6. Black spotted. The ratio of relative commercial abundance in the present new supply of these micas is approximately 1 C & SS to 4 FS to ro GS to 14 S to whatever the

Jan 1, 1948

By Russell G. Wayland

This paper gives the author&apos;s personal idea of the general viewpoint of the world&apos;s largest mica consumer, the U. S. Army, toward the supply, uses, and conservation of mica. However, to cover so broad a subject in a brief paper will require the dismissal of many phases with little or no mention. For example, it will be necessary to omit further reference to phlogopite or amber mica, even though amber block and splittings for certain spark plugs and commutator segments present some supply problems. This paper will deal entirely with muscovite, or white mica. Muscovite Mica Muscovite mica is available commercially in four general forms; namely, as block mica, as splittings, as washer punch, and as scrap mica.1 No strategic importance is attached to washer punch and scrap mica, even though scrap has found some use in military construction and in electrical ceramics. The use of washer punch as such has fallen off with the non-manufacture of household electrical appliances. Some qualities of block mica are also of little or no interest, but other qualities of block mica and all splittings are considered of vital importance. Army equipment requires large amounts of muscovite mica splittings in the form of built-up mica commutator segments and coil insulation in motors and generators. Other military items using significant amounts of muscovite splittings are transformers, switchboards, and blasting apparatus. Flexible mica tape, made from bookform or loose-dusted splittings cemented to paper, linen, glass cloth, and other backing, is widely used in coil insulation in heavy electrical equipment and in aircraft generators. All muscovite mica splittings come from India, principally because of the enormous amount of hand labor required in their preparation. In this emergency, the need for them was anticipated and large industry and government stocks were on hand, while shipments have continued to come by sea in spite of wartime hazards. With the possible exception of certain bookform splittings, no trouble is anticipated in supply. Accordingly, the remainder of this paper is devoted to block (or sheet) muscovite mica, including condenser film that is split from block. The Mica Problem Block muscovite mica is commercially classified into the following general qualitie3, beginning with the best quality: 1. Clear and Slightly Stained (C & SS). 2. Fair stained (FS). 3. Good stained (GS). 4. stained (s). 5. Heavy Stained (HS). 6. Black spotted. The ratio of relative commercial abundance in the present new supply of these micas is approximately 1 C & SS to 4 FS to ro GS to 14 S to whatever the

Jan 1, 1948

By Homer F. Staley, C. P. Karr

The casting alloy 88 copper, 10 tin, 2 zinc, commonly known in England as Admiralty metal and in this country as Government bronze, gun metal, or Naval Department composition G, has, at its best, many valuable properties. However, its physical properties are known to vary widely with slight changes in method of manufacture of the castings, such as slight variations in composition, variation in pouring temperature, kind of mold used, method of pouring and gating of molds, size and shape of castings, amount and kind of heat treatment, and so forth.&apos; The microstructure of castings made from this alloy is influenced by slight variations of composition, rate of cooling, and kind and length of heat treatment. This is best understood by reference to the equilibrium diagram. The part of the diagram in which we are interested and the effect of the thermal equilibrium relations on the physical properties of the alloy 88 copper, 10 tin, 2 zinc, have been discussed by Hoyt, Campbell, Primrose, and Rawdon.2 In Fig. 1 is given the equilibrium diagram of the copper-tin alloys. Briefly stated, the relations of composition and temperature changes are as follows. Compositions between A and a consist of but one constit ent—the a bronze, which is a solid solution of copper and tin, rich in copper. On cooling from the molten state these compositions gradually crystallize, at temperatures above 790°, into a mass of interwoven treelike crystals or dendrites. The cores of the dendrites are rich in copper and the percentage of tin gradually increases as the surfaces are approached. AS cooling progresses, after a11 the metal has crystallized, no further changes occur in the crystals other than diffusion within the crystals, which tends to erase the dendritic pattern and to render the structure more homogeneous. * Metallurgical Ceramist, U. S. Bureau of Standards, Associate Physicist, U. 8. Bureau of Standards. A. D. Flinn: Iron. Age (1915) 96, 1292-3. C. P. Karr: U. S. Bureau of Standards Tech. Paper 59, Pt. 1. S. L. Hoyt: Enging. (1913) 96, 667-7, 704-5. William Campbell: Trans. Am. Inst. Met. (1912) 6, 158-172. H. S. Primrose: Metal Ind. (1916) 14, 202-4. H. S. Rawdon: U. S. Bureau of Standards Tech. Paper 59, Pt. 11.

Jan 1, 1921

By Robert Glass Cleland

IN gathering material for this book, I have made extensive use of the archives of Phelps Dodge, contemporary news- papers, and a wide range of secondary sources. Two manuscripts-one on the history of Phelps Dodge by Arthur Train, Jr., and John L. Lawler, the other a biography of William E. Dodge by Richard Lowitt-have been of the greatest value. I owe a particular debt to the authors whose names I have just mentioned. I have also gathered important information and obtained revealing points of view from conversations with many people. Personal visits to the company&apos;s mines and plants added knowledge and understanding that nothing else was able to supply. I am greatly obligated to the officers of the company, especially to Mr. Louis S. Cates, chairman of the board of directors, Mr. Robert G. Page, president, Mr. George R. Drysdale, vice-president of Phelps Dodge Corporation, and Mr. Walter C. Bennett, president of Phelps Dodge Refining Corporation, for their co-operation and assistance. Mr. Wylie Brown, former president of Phelps Dodge Copper Products Corporation, also supplied valuable data and deeply appreciated hospitality. In my visits to the Phelps Dodge properties, company representatives extended every hospitality and placed at

Jan 1, 1952

By J. C. Fisher

C. S. Smith has described a method for measuring the relative values of different solid-solid and solid-liquid interfacial tensi0ns. When a polyphase alloy is held at an elevated temperature, individual particles of each phase adjust their shapes and minimize the interfacial energy. Wherever three interfaces meet, the dihedral angles are such that the three interfacial tensions, considered as forces, are in equilibrium. When the angles between three forces in equilibrium at a point are known, it is possible to determine any two in terms of the third. In this way ratios of interfacial tensions have been .obtained. The value of a given interfacial tension ratio was found to be independent of the alloy system from which it was determined. Smith also has employed the method when one of the phases is liquid. When equilibrium is reached with respect to In the course of work on grain growth in high purity aluminum a simple optical method was developed for detecting the presence or absence of preferred orientation in annealed specimens. The specimens were prepared by grinding, polishing and "deep etching." The etching reagent used for high purity aluminum has been described.* The resulting etch pits produced selective

Jan 1, 1949

By J. Gross

G. H. Clevenger, Chairman of the Milling Methods Committee of the Institute, made the following introductory remarks: "Several years ago, a number of us felt that the time was ripe for a fundamental investigation of crushing and grinding. At the outset, it appeared that the first thing we needed was a yardstick whereby grinding efficiency could be measured. "The U. S. Bureau of Mines has been most generous in cooperating with the Milling Methods Committee in getting this work well under way. John Gross, who served the committee for a year as secretary, was placed in charge of the investigation and has been ably assisted by S. R. Zimmerley. "Messrs. Gross and Zimmerley will now present the Progress Report covering their work to date." PROGRESS REPORT J. Gross, Salt Lake City, Utah. -This has not been a simple problem, and when I tell you that we can give you a verbal report of what we have done during three years in five or ten minutes you will realize that we have necessarily done a great deal of work that does not appear in the final results. We have been in a virtually new field. Therefore, we have had to feel our way at each step so as to be fairly sure we were correct. The first thing that was realized in this problem was that unless we had some method of measuring what happened when we crushed an ore, we might as well quit and not go further. We realized that if we tried to measure the results of crushing or grinding by the ordinary sizing test we would not get anywhere. We could sieve down to say 200 mesh fairly accurately; we could even go one sieve size further with a little less accuracy, and then we were absolutely lost, unless we went into microscopic measurement. Even this latter method would not have been satisfactory. The question was: what were we going to measure? If we were going to measure size, we might measure one particular dimension of a particle and be off 200 per cent. or more. If we tried to measure surface, we would have something tangible; the surface of a particle, no matter how irregular, is something definite, far more definite than any linear dimension would be. Moreover, if we could measure surface, we would immediately have a method of checking the Rittinger law as to whether it was or was not correct. So the first thing that we sought was a method whereby we could measure surface on crushed particles or, we will say, on particles; it would not make any difference whether crushed or not. It then became a question of what kind of particles we were going to use in obtaining a method for surface measurement. We realized that it would be rather a com-

Jan 1, 1928

By Claude P. Heiner

mountain region to M tht Coast points for domestic consumption and for export are shown in Table 11. There is considerable disparity in rates from both Rock Springs, Wyo., and Castle Gate, Utah, to the four coast cities where the slack coal is to be used for purposes other than export. The rate on coal to be exported is the same from either starting point to any of the four coast cities even though there is a difference of as much as 341 miles in the shipping distance. It is interesting to note that the freight rate between Sunnyside, Utah, and Fontana, Calif., on coking coal is $5.05 per ton and that coal up to 8 in. can be moved on this rate if it is suitable for coking. This rate was published late in 1942 on a contemplated annual movement of more than 500,000 tons. There have been decreases in freight rates since 1923 on movements of slack coal from Utah into Seattle and Portland due to pressure on the railroads and to greater. quantity of coal shipped. It is the author,&apos;, opinion that a movement of slack coal in excess of 3 million tons of coal per year from Utah to any point in central California would justify a freight rate equal to that puhlished for Fontana, Calif.. or $5.05 per ton. The movement of 3 1/2 million tons of coal per year on the basis of 240 mine working days per year would require that 14,600 tons be handled each mine working day. If it is assumed that shipments could be arranged for a 6-day week, the average railway movement would he 11,200 tons, or approximately 3 trains containing fifty-five 70-ton coal cars per day. Such movements of coal would require railroad equipment represented by the investment amounts stated in Table 12 and entail the services of 250 men. Table 12 ... Railroad Equipment and Investment Required To Move 11,200 Tons of Coal a Day from Utah to California Railroad Equipment Cost 2800. 70-ton coal cara at $6.000 each $16,800.000 32 locomotives at $310.000 each. 9.920.000 Miscellaneous eauiument:.......... .5;000:000 Total........................ $31,720,000 It therefore appears that, under presently known mining methods, the lowest price at which coal could be sold f.0.b. the mine in amounts of 3 1/2 million tons per year for generation of power in central California would be $4.60. It also appears that the lowest freight rate that could be expecled between intermountain points and the central California area would be $5.05 per ton, making a total cost of coal delivered at a plant site of $9.65 per ton. Conelusions The following are the author&apos;s conclusions: 1. Coal mines in Utah and in the Kemmerer and Rock Springs districts of Wyoming could increase annual production by 6 1/2 million tons per year. 2. Under present conditions coal could probably be delivered to any steam electric plant in central California at a price not to exceed $9.65 per ton. 3. The use of coal at such a price, while higher than the equivalent present price of fuel oil, is entirely feasible. 4. There are adequate railroad facilities for movements of large quantities of coal from the intermountain region to the Rest Coast. 5. In a national emergency it probably would be extremely difficult, if not impossible, to obtain sufficient oil to meet requirements of the greatly expanded West Coast steam electric generatsing capacity. 6. The intermountain region contains ample coal reserves to supply all conceivable demands for West Coast power generation for a number of generations. 7. Increasing demands of labor threaten to lessen, if not eliminate, savings in cost of coal production through the use of new mining machinery. 8. Continuation of experiments in socialism by the Federal Government through construction of hydroelectric generating plants, particularly those unrelated to land-use reclamation, defies justification. Rates under this concept of a governmental function are subsidized through greater taxation of its people. Private capital is available to construct steam plants, or hydro plants where feasible, and should be permitted to continue in order to preserve the principles of our free enterprise system. DISCUSSION (L. C. McCabe and Robert P. Koenig, presiding) C. C;. BALl*—I was asked to lead off the discussion, but it is not with the thought that I might be able to add anything to the paper. The thoroughness with which it was prepared rather forestalls the asking of many questions. Your treatment, Mr. Heiner, is a very valuable contribution. I do want to suggest—that although you have limited your study to this specific question, with certain geographic limitations, many of the things in your paper apply just as well to the eastern coals. I want to agree 100 pct with your final conclusion concerning government-subsidized construction. Id. C. McCabe*—It is certainly worthwhile to take stock occasionally to see where we are going in problems of this nature. I agree with Mr. Heiner that ultimately the only reliable source of fuel that the West Coast has is coal hut the time factor is the difficult element to evaluate. Just before I came here I discussed this subject with N. B. Hinson, Vice President and Executixe Engineer of the Southern California Edison Company, and Chairman of the West Coast Inter-Power Exchange Committee. He has given much thought to utilities&apos; fuel supply and it was very helpful to me in preparing a discussion of the paper to talk with him beforehand. Stock taking and forecasting of future development are essential to the continuing success of any enterprise. Mr. Heiner has called attention to the unprecedented growth of central and southern California and to the increased demands for fuel and power which have accompanied it. He discusses the increased fuel oil and natural gas requirements and the probable limits on the future use of these fuels and of hydroelectric power. In contrast to the calculable limits of these sources of electric energy, the author points to the availability of enormous reserves of coal in the Rocky Mountain States adjacent to the Pacific Coast which can be utilized for power generation. That there will be increased use of coal for power generation in the area under discussion is generally accepted hut it is in the timetable of such development that there is not complete agreement. In a recent report, Mr. Hinson reviewed the future power outlook for the Pacific southwest area. He pointed out that the use of steam plants in connection with water power plants in this region has made the maximum use of hydroelectric energy possible, and that the correct balance between hydro and steam generating plants produces the most economical overall system. Steam plants in the area which had been installed to protect against deficiency in hydro energy in dry years were used to carry war loads. Fortunately, no dry

Jan 1, 1950

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith&apos;s data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy&apos;s obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:&apos;l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world&apos;s produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world&apos;s demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world&apos;s barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

By J. N. Ong, J. P. Ratledge, J. H. Boyce

Since German operators opened the Tsumeb mine in the early 1900&apos;s, continuous operation has been interrupted only by enforced shutdowns during two world wars and the depression of the 1930&apos;s. Original metallurgical practice was blast furnace smelting. This was applicable only to low zinc ore, leaving large tonnages of high zinc ore to be stockpiled on the surface. A gravity concentrator using tables, buddles, and jigs operated for several years, but differential flotation of the ore did not get beyond the experimental stage. When the property was put up for sale by the South African Custodian of Enemy Property there was an estimated 434,000 tons of ore on surface dumps. The dump material, assaying 4.48 pct Cu, 15.8 pct Pb, and 10.9 pct Zn, had become highly oxidized during a stay of many years on the surface. But these dump ores had to be used in evaluating possible metallurgy because the shaft became flooded after the 1940 shutdown and underground ore was unavailable. Many companies examined Tsumeb but quickly lost enthusiasm because of the formidable metallurgical problems presented by the dump ore. However, on the basis of extensive test work, the present company decided that differential flotation would be successful and purchased the property after competitive bidding.

Jan 4, 1955

By M. E. Wadsworth, P. H. Yu, C. K. Hansen

A study of the rate of dissc5lution of chalcopyrite (CuFeS2) in acidic solutions under oxygen overpressures was carried out by measuring the rate of formation of cupric ions in solution. Effects of temperature, oxygen partial pressure, surface area, and concentration of sulfuric acid were evaluated. A sized batch of chalcopyrite was leached in the temperature range of 125° to 175°C and in the pressure range of 75 to 400 psi of oxygen. In 0.5 N H2SO4 all products of reaction went into solution except for trace amounts of elemental sulfur. The dissolution of chalcopyrite followed linear kinetics and was essentially independent of hydrogen ion concentration for H2S04 concentrations between 0.2 and 0.5 N. The oxygen dependence indicated adsorption approaching limiting values with increasing oxygen pressure. The linear mechanism was explained in terms of steady-state adsorption of oxygen at the chalcopyrite surface followed by a surface reaction. The enthalpy of activation for adsorption of oxygen was found to be approximately 33 kcal per mole. An activation enthalpy of approximately 9 kcal per mole was observed for the surface reaction. Charge transfer reactions are not rate controlling in the process.

Jan 1, 1973

By R. E. Ogilvie, A. R. Kaufmann, S. H. Gelles

The solid-solubility limits of iron in beryllium were determined between 850o and 1200oC by analysis of differential type multiphase diffusion couples, using an X-ray absorption technique. The maximum value of the solubility limit was found to be 0.92 ± 0.02 at. pct (5.46 wt pet) at the eutectic temperature 1225°C. The solubilities of nickel and beryllium were determined between 900°and 1200°C by the same technique and the maximum solubility was found to be 4.93 + 0.01 at. pct (25.2 wt pet) at the eutectoid temperature, 1065°C. A previously unreported high-temperature phase which decomposes eutectoidally at 1065 °C was found to exist in the beryllium-nickel system at a composition of approximately 8 at. pct Ni (36 wt pet) by diffision-couple analysis. The presence of this phase was confirmed by thermal analysis and metallo-graphic analysis of the structure resulting from the eutectoid decomposition. G. V. Raynor1 has treated the solid solubilities of some of the elements in beryllium on the basis of the "Hume-Rothery" rules2 which have been modified to include ionic size and ionic distortion effects. It was predicted that the solubility of iron and nickel in beryllium should be slightly less than that of copper. The lowering of the solubility, according to Raynor, is due to a more unfavorable relative valency effect and an ionic size effect. Kaufmann and corzine3 have compiled data on the solubilities of elements in beryllium and have discussed them in the light of the Raynor paper. These authors feel that, because the elements having the greatest solubility in beryllium systematically fall in the Group VIII and IB Columns of the periodic table, the electronic structure greatly influences the maximum solid solubility of elements in beryllium. The solubility of iron in beryllium was determined by Teitel and cohen4 as part of the study of the beryllium-iron phase diagram. The determination was carried out by X-ray and thermal analysis and according to the phase diagram presented, the maximum solubility of iron in beryllium is 0.41 at. pct (2.5 wt pct) at 1225oC. However, it is estimated that the uncertainty in the position of the a-beryllium primary solid-solution boundary is about 0.5 at. pct (3wtpct). Losana and Goria3 in studying the beryllium-nickel phase diagram, determined the solid solubility of nickel in beryllium by thermal analysis. They found the maximum solubility to be between 1.65 and 2.65 at. pct (10 to 15 wt pct) at 1240°C. This value decreased rapidly with decreasing temperature. In determining approximate ranges of solubilities for different elements in beryllium, Kaufmann, et al,8 reported a value of between 1.3 and 1.7 at. pct (7.9 to 10.1 wt pct) for the solubility of nickel in beryllium. The value was obtained by metallographic examination of quenched alloys and lattice-parameter measurements. However, the authors also noted a single-phase structure for a 1.7 at. pct Ni alloy (10 wt pct) on cooling from the liquid. This would indicate a higher solubility range than was reported. ~isch,&apos; in his X-ray studies of beryllium-copper, beryllium-nickel, and beryllium-iron intermetallic compounds, reports the disappearance of a second phase (Ni,Be2) in the beryllium primary solid solution at approximately 4 at. pct (20 wt pct). THEORY The analysis of concentration gradients in diffusion couples has proven to be a useful tool in determining phase equilibria.8-14 In this particular study the diffusion couples were chosen to straddle the expected composition range of the phase boundary, then heat treated at a given temperature and the concentration gradient evaluated. The composition of the phase boundary for a given temperature appears at a point of discontinuity of the composition gradient. Examples of typical phase diagrams and the concentration gradients which should be found in such systems are shown in Fig. 1. In the present work, gradients of the form of Fig. l(c) were obtained in diffusion couples made of pure beryllium and two-phase alloys of beryllium with either iron or nickel. The composition at the point where the gradient becomes discontinuous, Cs, corresponds to the solubility limit of either iron or nickel in beryllium. The analysis of the concentration gradients was carried out by an X-ra absorption method developed and applied by Ogilvie and later used by Moll13 and Hilliard.l4 It depends on the fact that the absorption of X-rays by matter is determined by the concentration and type of the various atomic species present. The relationship for the intensity, I, of a monochro-

Jan 1, 1960

Arkansas Geological Survey, Rooms 443-447 State Capitol, Little Rock, Ark George C Branner, State Geologist A list of available publications will be sent upon request Publications issued by the U. S Bureau of Mines, U S Geological Survey and Oklahoma Geological Survey, pertaining to&apos; Arkansas, are also available through this Survey office. Annual Reports may be had for the following years. 1890, 3147, 1891, 81 35; 1892, $1 10 Other available publications: The slates of Arkansas, by A H. Purdue, with a bibliography of the geology of Arkansas by John C Branner (1909), $1.10, Coal mining in Arkansas, pt 1, by A A Steel (1910), 3175, An outline of the physical features of Arkansas, by George C Branner (1927), free, An outline of the metallic minerals of Arkansas, by George C Branner, free, Bulletin 3, The geology of the Arkansas Paleozoic Area, by Carey Croneis (1930), $3 20, Bulletin 4, St Peter and older Ordovician sandstones of northern Arkansas, by A W Giles (1930), $1 95, Bulletin 5, A geomagnetic survey of the bauxite region of Arkansas, by Noel H Stearn (1930), 80 cents, Information Circular 1, A barite deposit in Hot Spring County, by B Parks and George C Branner (1932), $1, Information Circular 2,

Jan 1, 1933

By A. A. Smith, J. S. Smart, A. J. Phillips

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941