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By AIME AIME

BY COMBINING the sessions on reduction and refining of copper, lead and zinc it was possible to devote an entire day to nonferrous metallurgy. Four interesting papers were presented at the morning session and four more in the afternoon. In the discussion of papers on copper, F. R. Pyne acted as chairman, with H. M. Shepard as vice-chairman, whereas for those on lead and zinc, F. F. Colcord acted as chairman, with C. R. Hayward as vice-chairman. The paper by P. D. I. Honeyman on the smelting of raw concentrates in the reverberatory furnace was presented by Mr. Pyne and discussed by Messrs. Mazany and Hayward. The interesting paper by E. S. Bardwell, com- paring the use of various fuels in copper-refining furnaces at Great Fails, Mont., was presented by Mr. Shepard and discussed by Messrs. Boggs, Gronningsater and Hayward. That by R. G. Knickerhocker, describing the stationary basic copper converter at Messina, Transvaal, was presented by Mr. Pyne, together with a written discussion by c. R. Kuzell, of the United Verde Copper co. It was an interesting illustration of how well-known processes may sometimes be modified to fit into unusual conditions.

Jan 1, 1932

The personnel of the. Naval Advisory, Board on Inventions, of which Thomas A. Edison is to, be Chairmen, has- been announced. by' Secretary of the Navy Daniels, as follows: W. R. WHITNEY L: H. BAEKELAND American Chemical Society. FRANK JULIAN SPRAGUE, American Institute of Electrical Engineers. B. G. LAMME ROBERT SIMPSON WOODWARD ARTHUR GORDON WEBSTER American Mathematical Society. ANDREW MURRAY HUNT American Society of Civil -Engineers. ALFRED CRAVEN MATTHEW BACON SELLERS American Aeronautical Society. -HUDSON MAXIM PETER COOPER HEWITT Inventors' Guild. THOMAS ROBINS . HOWARD COFFIN ANDREW L. RIKER J American Society of Automobile Engineers. WILLIAM. LAWRENCE SAUNDERS American Institute of Mining BENJAMIN BOWDITCH THAYER Engineers. ? JOSEPH WILLIAM RICHARDS American Electrochemical Society. LAWRENCE ADDICKS WILLIAM LE. Roy EMMET American Society of Mechanical Engineers. SPENCER MILLER HENRY ALEXANDER WISE WOOD American Society of Aeronautic ¬ELMER AMBROSE SPERRY Engineers. ?

Jan 10, 1915

By H. E. Cline

Calculations of the formation and growth of faults caused by a variation in lumellar widths were made for a two-dimensioml three-plate problem. The angle between the a-ß boundary and the growth direction was allowed to vary and the time evolution was studied using a quasisteady state approach. At spacings smaller than a critical spacing given by X V = AO variations in the larrlellar widths grow in time to produce faults that coarsen the structure, while at spac-ings larger than this critical spacing, variations in the lamellar widths decay in time. If small plates are introduced into the structure they may grow only at large spacings to refine the structure. The time evolution and shape of faults were calculated for the three plate-problem and then the three dimensional problem and rod-like eutectic were qualitatively discussed. UNDERSTANDING of the mechanism by which the spacing of directionally solidified eutectics is determined may allow one to control their structure better. Steady state solutions for the growth of lamellar structures have been found for a range of lamellar spacings A and growth velocities V. To obtain a unique solution for the isothermal growth of pearlite, Zener1 assumed that growth occurs at a maximum velocity, while Tiller2 assumed that a eutectic alloy, grown under an imposed velocity, will choose a spacing corresponding to minimum undercooling. These assumptions are equivalent and have been referred to as "extremum growth". The extremum condition predicts the observed relation between velocity and spacing as given by V = constant [I] but does not provide a mechanism for changing the lamellar spacing. Jackson and Hunt3 calculated the interface shape by using solutions to the diffusion equation for a planar interface and a relation of the interface composition to the local curvature. If the spacing is much larger than the extremum spacing, the interface breaks down catastrophically to form forked plates. However, the catastrophic breakdown cannot account for the small adjustments in spacing that must occur in practice..3 Direct observations during the growth of organic eutectics4 and the Pb-Sn eutectic5 show that spacing changes occur by the formation of faults. A fault in a plate-like eutectic is the edge of a plate. Once the faults form, they may move to make small adjustments in the spacing.6,3 The motion of faults intersecting the growing interface was shown by an approximate analysis to give Eq. [I].6 A perfectly regular lamellar structure should be able to persist over a range of lamellar spacings. However, during growth small perturbations in the structure may occur. If the amplitude of the perturbation increases in time the structure is unstable, while if all possible perturbations decrease in time the structure is stable. In a previous paper7 variations in the shape of the solid-liquid interface were considered, while this paper considers only variations in lamellar widths while maintaining a macroscopically planar solid-liquid interface. Previously, theories of lamellar growth1"3 have artificially contrained the growth to give a regular periodic structure. To allow for a variation in spacing, the three phase intersections and groove angles were allowed to change with time as determined by assuming local equilibrium. THREE-PLATE PROBLEM Since the spacing changes in eutectics by local formation of faults,4'5 it is suggested that local variations in spacing are responsible. The interaction between neighboring plates will be greatest because they have the smallest diffusion distance. For simplicity, as a nearest neighbor approximation, a three-plate problem will be considered, as illustrated in Fig. 1. The structure consists of a periodic array in which all the plates are allowed to vary in width. As in steady state growth it is assumed that the average composition in the solid remains constant. A variation in plate widths, that maintains the composition in the solid, was introduced by making the first a-phase plate thinner by an amount A, keeping the width of the second B-phase plate constant, and increasing the width of the third a-phase plate. If the structure were not perturbed, as in the regular two-plate problem previously described,' then the groove angles at the three-phase junctions are the equilibrium angles, 0, and ? B, and the solid-solid boundary is normal to the interface. In the three-plate problem with a variation in plate widths the phase boundaries are assumed to be related to the three-phase junction by equilibrium angles, but the a/B boundaries may be rotated by an angle 0 from the growth direction. The angle H be-tween the tangent to the a/B boundary and the growth direction may vary during growth and determine the —> — — —.A_ Q-0 / 0 x, X2 Fig. 1—Schematic of the three-plate problem showing a variation in the spacing and the effect on the angles at the three phase intersections.

Jan 1, 1970

By H. Foster Bain

I. INTRODUCTION. By H. FOSTER BAIN.+ THE recently aroused public interest in the conservation of our natural resources has peculiar importance to mining-men, since they deal with resources which are stored products. Within certain limits, the fertility of a worn-out soil may be restored, deforested areas can be replanted, one year's wasted water-supply is followed by another; but coal and ores, once taken out, cannot be mined again, and should therefore be conserved with especial care. This means, however, not that mining should be restricted, but that it should be done most economically and with the minimum of waste.

Nov 1, 1908

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By Ashok K. Sinha

The quasi-binary systems "VFe3"—VCo,—VNi,— "VCu3"and "TiFe3"—TiCo3,—TiNi3-"TiCu3"have been studied by a combination of microscopic and X-ray methods. Of the Phases encountered, eleven had close-packed ordered layer structures. Within each system, there is an approximately linear variation of the degree of hexagonality of the stacking arrangement with electron concentration, e/a. A study of eighty -four known examples of AB3 structures in transition metal alloys indicates that at e/a = 8.65 the ordered structure of the close -packed layers changes from "triangular" (AuCu3 type) to "rectangular" (SbCu3 type). At e/a < 8.65, the slope of hexagonality us e/a line increases with the group number of the A component. An interesting series of close-packed ordered structures is known to exist at the composition AB3; however, their alloy chemistry has not yet been fully understood. Dwight and Beck1 observed a correlation between position of the components in the periodic table and the type of crystal structure of the binary AB2 structures formed by transition metals. No consistent effect due to atomic size was noted and they proposed that electron concentration* predominates in In the present paper, the AB3 structures are characterized by a symbol describing the stacking and a symbol specifying the ordered layer. The stacking symbol used was introduced by Zhdanov,7 and later used in the International Tables,8 and by Beck9 in his survey of possible layer stacking structures. Alternating positive and negative integers are used to represent the number of positive (e.g., in abcabc...) and negative (e.g., in cbacba...) stacking sequences. T denotes the triangular ordering found in close-packed planes of the AuCu3 structure and R the rectangular ordering found in close-packed planes of the SbCu3 structure, Figs. 3(a) and (b). The present structure symbols are listed in Table I alongside the prototypes, where known, and other structural characteristics of AB3 phases found in the present investigation. EXPERIMENTAL The starting materials were metals of 99.9+ purity. The alloys were prepared by arc melting under argon atmosphere using a nonconsumable tungsten electrode and water-cooled copper hearth. The total weight loss upon melting and subsequent annealing was always less than 0.5 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. The alloys were homogenized and annealed at suitable temperatures in the range 750" to 1200°C, the annealing periods varying from 3 days at 1200°C to 10 days at 750°C. The heat treatments were carried out in sealed silica capsules under argon atmosphere and with a molybdenum foil cover between the alloy and the walls of the capsule. The quenched alloys were microscopically examined and reduced to powder by crushing or filing. The powders were, whenever necessary, given a stress-relieving anneal at the original annealing temperature. X-ray powder patterns were obtained with an asymmetrical focusing camera, a Guinier-deWolff focusing camera, or a Debye-Scherrer camera. Cr, Co, or Cu radiations were used. In some cases, to ensure the minimum degree of contamination, the deeply etched specimens were mounted in the asymmetrical focusing camera to obtain an X-ray pattern. Internal silicon standards were employed for lattice parameter determinations. The intensity calculations were made by using a Fortran IV program

Jan 1, 1970

Organization Place Date 1919 American Chemical Society Philadelphia, Pa. Sept. 2-6 National Assn. of Stationary Engineers Huntington, W. Va. Sept. 8 American Peat Society Minneapolis, Minn. Sept. 22-24 American Iron, Steel Electrical Engineers St. Louis, Mo. Sept. 22-26 American Institute of Min. and Met. Engineers. Chicago, Ill. Sept. 22-27 American Steel Treaters&apos; Society, First Annual Convention Chicago Ill. Sept. 22-27 National Exposition of Chemical Industries.... Chicago, Ill. Sept. 22-27 National Safety Council Cleveland, O. Sept. 29-Oct. 2

Jan 8, 1919

By F. H. Turan, F. W. Jessen

The gel strength and viscosity of two different suspensions of fractionated montmorillonite clay were measured by using a Stormer viscosimeter and Farm V-G meter. The amount of sodium poly-phosphate (sodium bexametaphosphate, sodium tetraphosphate and sodium acid pyrophosphate) adsorbed by the clay particles was determined. A relationship seems to exist between the amount of polyphosphate adsorbed and the nature of the surface, edge or plate, assumed to be the principal sites for selective adsorption. Reduction in viscosity and gel strength was found to be directly related to the adsorption. Both chemical bonding and physical adsorption seem involved in defloccula-tion Some indication of the axial ratios of particles of .l- to .04-micron average size is possible though study of the adsorption mechanism. INTRODUCTION AND PURPOSE A knowledge of surface areas of clay particles in a suspension and a precise determination of phosphate adsorption should provide a basis for a better understanding of reduction in viscosity and gel strength caused by molecularly dehydrated phosphates. The purpose of this investigation was to study the adsorption of sodium polyphosphates on suspensions of fractionated sodium montmorillonite. Although there is considerable uncertainty regarding details of the structure of montmorillonite, a generally accepted one is that suggested by Hofmann, Endell and wi1m.l The structure shown in Fig. 1 is an idealized one, and Marshall2 has postulated that it is possible for several isomorphous replacements to occur. Thus, aluminum may replace silicon, in which case an exchangeable cation would go along with the aluminum to neutralize what would otherwise be a net negative charge on the structure. There is disagreement among various investigators as to the particle size and shape of montmorillonite clays. Marshall2 reported the following results for the mean lateral dimensions of a Putnam clay (montmorillonite)— 3,730 A° for particles having average diameters ranging from 500 to 1,000 A, and 750 A° for those with an average diameter less than 200 A. The latter particles were estimated at 50A°in thickness, which would correspond to a stack of five unit cell layers. On the other hand, Shaw3 has interpreted micrographs as indicating that particles of montmorillonite ire readilv broken down to the individual cell layers by dispersion in water. Brindley4 and Merings indicate the ultimate particles to be of the order of 300 A° in mean lateral dimension. Van Olphen6 suggested the thickness of particles at four to five unit cell layers. It was suggested also that this number tends to become smaller with increasing dilution. Recently, Kahn and Lewis7 determined the size of sodium montmorillonite particles in aqueous suspension from electro-optical bi-refringence decay curves. The

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.&apos; It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1905 * ABE, MASAYOSHI 1909 1903 * ADAMS, CHARLES C. 1905 1905 * ADAMS, WILLAMS 1909 1903 * ADAMS, W. EDWARDS 1910 1884 *ADDY, MATTHEW 1896 1889 * AKERS, WILLIAMS 1906 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 *AMIOT, H 1892 1886 *AMSLER, CARL 1894 1895 *ÅNGSTROM, CARL 1901 1887 * ARCHBALD, JAMES 1910 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUSTEN, PETER T 1907

Jan 1, 1917

By W. L. Fink, H. C. Stumpf, L. A. Willey

VERY few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.l0 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. MATERIALS The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society.4 Chemical analysis of the aluminum showed the following impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectrographic standard procedures5 No. IIA and No. SII respectively. DETERMINATION OF LIQUIDUS The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano.6 As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 ½ -in. iron pipe and pipe caps. The space around the sides of the crucible was filled with 40 mesh crystalline alundum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1948

By Park Wright

The fact that granite has been encountered by the drill by those in search of oil and gas in Kansas is becoming more and more a matter of interest, not only to the oil producer but to everyone directly and indirectly connected with the oil business. It is, therefore, time that someone should offer an explanation for its presence and form a definite opinion, based on all the data available, in regard to the effect it will have on the future prospects of the area affected as probable oil-and gas-producing territory. At present there seems to be no consensus of opinion. To the writer&apos;s knowledge, only one attempt has been made to explain ; by Erasmus Haworth, State Geologist of Kansas, in a paper entitled Bulletin Number Two on Crystalline Rocks in Kansas. The purpose of the present paper is to offer a theory for the presence of the granite, and to draw conclusions which will aid in determining the prospective oil and gas value of the area in question. In taking up this question it will be well to consider first the tests in which granite has been reported, with a general history of each. The accompanying map (Fig. 1) shows the location of all wells described. The first well in which granite was reported was that drilled just south of Zeandale in section 27, township 10 south, range 9 east, by a local company which had taken up a block of leases in that vicinity. At a depth of 958 ft. (291.99 m.) granite was encountered. Drilling was continued to a depth of 1093 ft. (333 m.) in the same formation, at which depth the hole was abandoned. Another well was started 1 mile east of the first well and the same rock was found at a depth of 945 ft. (288 m.). Drilling was continued to a depth of 1200 ft. (365.76 m.) with the bit in the same formation. Samples of the drill cuttings have been examined and they are undoubtedly crushed granite. The next well in which granite was found was that drilled by DeLaat and Shepard, independent wildcat operators, in section 34, township 19 south, range 7 east, near the town of Elmdale. Granite was struck at 1707 ft. (520 m.) and the hole was abandoned in the same formation at 2525 ft. (769 m.). Mr. DeLaat watched the drilling of this well very closely and he has described to me in some detail the formation immedi-

Jan 1, 1918

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.&apos; The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By Park Wright

THE fact that granite has been encountered by the drill by those in search of oil and gas in Kansas is becoming more and more a matter of interest, not only to the oil producer but to everyone directly and- indirectly connected with the oil business. It is, therefore, time that someone should offer an explanation for its presence and form a definite opinion based on all the data available in regard to the effect it will have on the future prospects of the area affected as probable oil- and gas-producing territory. At present there seems to be no consensus of opinion. To the writer&apos;s knowledge, only one attempt has been made to explain; by Erasmus Haworth, State Geologist of Kansas, in a paper entitled Bulletin, Number Two on Crystalline Rocks in Kansas. The purpose of the present paper is to offer a theory for the presence of the granite and to draw conclusions which will aid in determining the prospective oil and gas value of the area in question. In taking up this question it will be well to consider first the tests in which granite has been reported, with a general history of each. The accompanying map (Fig. 1) shows the location of all wells described. The first well in which granite was reported was that drilled just south of Zeandale in section 27, township 10 south, range 9 east, by a local company which had taken up a block of leases in that vicinity. At a depth of 958 ft. (291.99 m.) granite was encountered. Drilling was continued to a depth of 1,093 ft. (333 m.) in the same formation, at which depth the hole was abandoned. Another well was started 1 mile east of the first well and the same rock was found at a depth of 945 ft. (288 m.). Drilling was continued to a depth of 1,200 ft. (365.76 m.) with the bit in the sane formation. Samples of the drill cuttings have been examined and they are undoubtedly crushed granite. The next well in which granite was found was that drilled by DeLaat and Shepard, independent wildcat operators, in section 34, township 19 south,. range 7 east, near the town of Elmdale. Granite was struck at 1,707 ft. (520 m.) and the hole was abandoned in the same formation at 2,525 ft. (769 m.). Mr. DeLaat watched the drilling of this well very closely and he has described to me in some detail the formation immedi-

Jan 8, 1917

By M. G. Benz, J. F. Elliott

A new type of solution calorimeter has been constructed to measure heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction at temperatures above 1000°C. With it, measurements hove been made of the partial molar heats of mixing joy tin in the Cu-Sn system from 0 to 13 at. pet Sn at 1127°C and fir nickel in the Cu-Ni system from 0 to 9 at, pet Ni at 1200°C. The integral molar heat of mixing for the Cu-Sn system is strongly negative with a calculated minimum value corresponding to the composition Cu3Sn. The integrnl molar heat of mixing for the Czi-Ni system is slightly positive at these temperatures. These integral molar values have been measured with a probable error less than 30 cal per g-atom at an atom fraction of nickel or tin equal to 0.1. The estimated probable error for the Cu-Sn system is approximately 450 cal for a measured heat of solution of approximately 9000 cal. For the Cu-Ni system it is approximately 700 cal for a measured heat of&apos; solution of approximately 60 cal. A new type of heat of solution calorimeter was designed and constructed to provide a more accurate experimental method for determining heat effects at high temperatures, (T > 1000°C). With it, partial molar heats of mixing, enthalpy increments, heats of fusion, and heats of formation and reaction for metal systems can be measured directly. Previously it has been necessary to rely upon the use of the dropping calorimeter or the van&apos;t Hoff equation applied to equilibrium data for this information. For the most part equilibrium data are scarce and difficult to obtain in many cases, and it has been necessary to rely upon the "method of mixtures" for the desired enthalpy measurements. An earlier study1 provides a prototype for this work. The "method of mixtures" as outlined by K. K. kelley,2 "consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a calorimeter operating at or near room temperature.&apos;&apos; In this manner the change in the total heat content (enthalpy) of the substance between the temperature of the furnace and that of the calorimeter is determined. In order to determine high-temperature heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction, it is necessary to take the difference between two such measurements, one before and one after the occurrence of the enthalpy change being studied. The desired enthalpy change is then the small difference between two large numbers. Small errors in the large numbers are included as large errors in this small difference. It is this difficulty that must be avoided for accurate measurement of the desired functions. The procedure with the new solution calorimeter consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a solution calorimeter operating in the temperature range of 1000o to 1200°C. Measurements in the range of 1200" to 1600°C are planned for the future. By selection of the composition and

Jan 1, 1964

By L. M. Howe, J. Gordon Parr, E. Saarema

THE decreasing solid solubility limit at the titanium-rich end of the Ti-Cu constitutional diagram,&apos; Fig. 1, suggests the possibility that titanium-rich alloys may be age-hardenable. However, results obtained by Holden et al. reproduced in Fig. 2 show that after quenching from 790°C the age-hardening of an alloy containing 1.7 pet Cu is very slight, while a 0.8 pet alloy decreases in hardness, during heat treatment at 400°C. It was believed possible that powder samples of alloys might show different results from the lump samples used by Holden et al., since small particles are often more sensitive to diffusion processes than larger samples. Consequently, a 1.9 pet (by weight) Cu alloy was made by the technique of levitation melting," checked for homogeneity, and filings of 48-65 Tyler screen size were cut from it for aging experiments. The filings were helium-quenched (by a technique described previously)&apos; from 790°C, sealed in vacuo in silica tubes and aged at temperatures of 400°, 450°, and 500°C. Microscopic and X-ray examinations failed to reveal any structural changes during the aging process. This is not too surprising since early stages of precipitation do not usually manifest themselves in ways that are readily detectable by metallographic methods, and the extent of precipitation on overaging a 1.9 pet alloy is very small. However, hardness readings (taken on a Bergs-man micro hardness tester, using a 25 g load applied to a diamond indenter) do show a hardness peak at each aging temperature, Fig. 3. About a dozen readings were taken on each heat treated sample; the highest reading and the lowest reading were ignored and an average taken of the remaining values. In

Jan 1, 1957

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

By J. C. Allen, E. V. Herring

CHILE EXPLORATION CO&apos;s. oxide plant at Chuquicamata, the largest of its kind, started in 1915 with initial operations at the rate of 10,000 tons of ore per day. Anaconda Copper Mining Co. acquired the controlling interest in 1923 and in the next few years modernized the plant and mine, extending operations to a nominal capacity of 490 million lb of electrolytic copper yearly by 1942. Plant production averaging 495.7 million lb of copper per year was maintained for the eight-year period extending from 1941 to 1948 inclusive. During the World War II production reached its highest level when in 1944 the output was 531.8 million lb. The maximum production for any one month was 49.6 million lb, achieved in May 1947. E. A. Cappelen Smith, consulting metallurgist for M. Guggenheim&apos;s Sons, worked out the first process for the treatment of Chuquicamata copper oxide ore about 1913, and directed a staff of 20 young engineers operating a pilot plant at Perth Amboy, N. J., on three shifts for an entire year. The copper is extracted from the oxide ore by a hydro-metallurgical treatment described in detail by T. A. Campbell in AIME Transactions, Vol. 106, Copper Metallurgy, 1933. The Oxide Plant is divided into five main operations as follows: (1) Crushing, (2) Leaching, including dechloridizing and sulphur dioxide treatment, (3) Tailing disposal, (4) Electrolytic precipitation, (5) Smelting and melting. Crushing The present Primary Crushing Plant has been in operation 25 years, during which time 4,342,112 cars of 70 tons net capacity have passed through the dumpers. The ore as received from the mine is frequently blocky and up to 5 feet in section. It is reduced to 9-in. size by two 60-in. gyratory crushers, and transported to the east and west ore bins by 60-in. conveyors. In the secondary crushing operation the ore is first reduced to 2 to 3-in. size by five standard 7-ft cone crushers and two No. 10 gyratories. This product is then reduced to 3/8-in. size by fifty-two 48-in. vertical Symons disc crushers and is transported by belt conveyors to the loading bridges from which it is charged° into the leaching vats. Conveyor belt No. 14 which serves the eight vats in the east section of the leaching plant has transported over 125 million tons of ore, which is a record for any type of conveyor. This 60-in. belt travels at a speed of 600 fpm and carries loads up to 5500 tons per hr. Leaching The ore is leached in 14 vats, averaging 13,500 short tons net capacity each. These vats are lined with a natural mastic which adequately resists the sulphuric acid leaching solutions. The leaching process as presently conducted comprises soaking the ore with successive volumes of leaching solution and spent electrolyte and withdrawing successive volumes of enriched solution from the vat to a total of approximately 3.2 million gal. The first 1.6 million gal of this volume withdrawn is called strong solution and contains about 35 parts of copper per 1000. The balance of 1.6 million gal subsequently withdrawn is stored in a

Jan 1, 1952

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith&apos; and of A. G. H. Andersen .2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford," using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,1,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates h in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

By L. Burris, C. H. Stockman, I. G. Dillion

Zone melting is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Equations are presented which 1—predict the concentration profiles after successive passes of the zone and 2—give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing in the last zone length. These equations were solved numerically using an electronic computer, and the concentration profiles are presented as a function of the solute distribution coefficient and the ratio of molten zone to total bar length. ZONE MELTING is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Separation occurs if the solid freezing from a solution at any moment has a composition different from that of the liquid from which it is freezing. Solutes which lower the freezing point will tend to remain in solution and will be moved in the direction of zone travel. Solutes which raise the freezing point will preferentially freeze out, and they will be moved in a direction opposite to that of zone travel. After repeated unidirectional passage of a molten zone through a bar of material, impurities will be concentrated in the ends of the bar. A limiting concentration gradient will be reached in the bar after a large number of passes of the molten zone. Both the magnitude of this limiting concentration gradient and the rate of movement of solute in any pass depend on the zone length and on the equilibrium concentrations of solute in the liquid and solid phases. The basic theory of zone melting was thoroughly covered by Pfann.1 The purpose of this paper is to extend the theory of zone melting by presenting 1—equations which relate the concentration profiles in successive passes of the zone and 2—equations which give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing* in the last zone length concentration of a given solute in the solid to the concentration of the same solute in the liquid. Analytical methods for determining the concentration profiles after any pass have been developed by Lord2 and Reiss. The method developed by Lord does not take into account normal freezing in the last zone and also becomes very complicated when the number of passes becomes large. The method developed by Reiss enables the direct calculation of the complete concentration profiles (including that in the last zone) after any pass for values of k close to unity (0.9 < k < 1.1). Both methods are useful and provide valuable insight into the zone melting process. The equations given in this article are based on the same assumptions used by Pfann. These are: 1—uniform composition in the liquid, 2—negligible diffusion in the solid, 3—constant distribution coefficient, 4—constant length of the liquid zone (except at the ends), and 5—solubility of the solute in the melt is not exceeded at any point. Equations for Concentrations in Successive Passes For a melted zone of length 1 at the left-hand end of a bar of uniform unit cross-section, the amount of solute in the liquid is J0Cn-1(x) dx [1] where the subscript is the number of the pass. Cn-1(x) represents the concentration (expressed as weight per unit volume) obtained in the previous

Jan 1, 1956