Search Documents

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By A. M. Sarem

For the performance prediction of multiphase oil recovery processes such as steam stimulation, there is an acute need for three-phase relative permeability data. No fast and simple experimental technique, such as the unsteady state method proposed by Welge for two-phase flow, is available for the three-phase flow. In this paper, an unsteady - state method is presented for obtaining three-phase relative permeability data; this method is as fast and easy as Welge's method for two - phase flow. Analytical expressions are derived by extension of the Buckley-Leverett theory to three-phase flow to express the saturation at the outflow face for all three phases in terms of the known parameters. It is assumed that the fractional flow and relative permeability of each phase are a function of the saturation of that phase. Other simplifying assumptions made include the neglect of capillary and gravity effects. The effect of saturation history upon relative permeability is acknowledged and attainment of similar saturation history in laboratory and field is recommended. The required experimental work and computations are simple to perform. The test core is presaturated with oil and water, then subjected to gas drive. During the test, required data are the rates of oil, water, and gas production, together with pressure drop and temperature. The ordinary gas-oil unsteady-state relative permeability apparatus can be readily modified to measure the required data. The proposed technique was applied to samples of a Berea and a reservoir core. The effect of saturation history upon relative permeability was studied on one Berea core. It was found that increase in initial water saturation has a similar effect upon three-pbase relative permeability as it does in two-phase flow. INTRODUCTION In the light of increasing demand for three-phase relative permeability data for predicting the performance of thermal and other multiphase-flow recovery processes, a simple and accurate method of experimental determination of such data is extremely desirable. Leverett and Lewis 1 described the simultaneous flow method of obtaining three-phase relative permeability data. However, Caudle et al.2 reported that this method is very time consuming and cumbersome. Corey3 proposed calculating the three-phase relative permeability from measured krg data. Corey's theory is based on simplified capillary pressure curves,4 assuming a straight line relationship between I/Pc2 and saturation. Also, Corey's method assumes a preferentially water-wet system. The simplest and quickest method of obtaining three-phase relative permeability data is the unsteady-state method where, for instance, oil and water are displaced by gas. However, in such a test the correlation of average saturation with relative permeability does not give a valid relationship because the rates of oil, water and gas flow in the sample change continuously from the upstream to downstream end. This difficulty in calculating valid relationships was solved by Welge for two-phase flow by deriving an expression for determining the outflow face saturation from Buckley and Leverett frontal advance equations.5,6 In this paper, relations are established to determine the outflow face saturation and relative permeability to all phases in a three-phase flow displacement experiment. PROPOSED METHOD The fundamentals established by Buckley and Leverett5 for two-phase flow were extended to three - phase flow and used as a basis for the derivation of saturation equations. This approach is comparable to Welge's6 use of Buckley and Leverett theory in arriving at expressions to determine the outflow face saturation of the displacing fluid in a two-phase flow system.

Jan 1, 1967

By M. A. Dayananda

Based on the Kirkendall frame of reference, a method is proposed for the determination of atomic mobilities of all the diffusing species in a multicorn-ponent system with a single diffusion couple. The method is based on an atomic mobility model developed on the concept of negligible interactions among the intrinsic fluxes. It is shown in the model that mobilities can be obtained directly from the cumulative intrinsic fluxes past the Kirkendall interface. The proposed method replaces the need for a prior determination of interdiffusion coefficients far the calculation of mobilities. Relations between intrinsic diffusion coefficients and mobilities are derived and the mobility calculations are illustrated with diffusion data in Cu-Zn-Mn alloys at 850°C. ThE concept of "intrinsic flux" with respect to a fixed lattice was introduced "i Darken1 to explain toa Kirkendall effect2 demonstrated by the motion of inert markers during isothermal diffusion in single-phase binary solid solutions. Based on this concept, intrinsic diffusion studies have been made in various binary metallic systems3,4 employing such a lattice frame of reference, commonly referred to as the Kirkendall interface. Similar approaches, both theoretical and experimental, have been presented5"10 to study intrinsic diffusion in multicomponent systems. Based on the direct integration of Fick's law extended to multicomponent diffusion, Philibert and Guy8 proposed a method for the determination of intrinsic diffusion coefficients. For an n-component system, this procedure requires an experimental study with (n — 1) diffusion couples, all having their Kirkendall interfaces at the same compositio;, where n(n — 1) intrinsic diffusion coefficients are defined. This technique has been employed for ternary diffusion studies by Dayananda and Grace" and Guy and Leroy.11 A different approach is recommended by Ziebold and Cooper,12 who have derived relations between interdiffusion coefficients and atomic mobilities employing fluxes referred to the local center of volume. Their analysis is based on the simplifying assumption of negligible interactions among intrinsic fluxes. This assumption has been considered satisfactory for dilute solutions.5"7 The use of this analysis for the calculation of mobilities requires an initial determination of interdiffusion coefficients with a set of diffusion couples having intersecting diffusion paths. It is the purpose of this paper to propose a method that would permit a direct determination of mobilities of all components of a multicomponent system from a single diffusion couple. This method is based on a mo- bility model developed with diffusion fluxes referred directly to the Kirkendall interface, generally identified by inert markers. gen erall, like that of Ziebold and Cooper,12 employs the simplifying assumption that the flux of each component relative to a fixed lattice is caused only by the driving force of its own chemical potential gradient. THE KIRKENDALL INTERFACE Inert markers are employed in diffusion couples to locate experimentally the position of the Kirkendall interface. They are initially placed at the weld interface for "sandwich" couples, or at the original vapor-solid interface for vapor-solid couples. Studies of marker motion in binary systems3'4 with both types of couples indicate that markers remain in a plane of constant composition and move with this plane para-bolically with time. Parabolic marker movements were also observed in ternary Cu-Zn-Mn couples by Dayananda and Grace.10 It is reasonable to expect a similar marker behavior even for diffusion couples with a higher number of components.

Jan 1, 1969

THE Annual Fall Meeting held in Chicago in conjunction with the celebration of a Centennial of Engineering brought forth a round of field trips and symposiums which did much to add to the store of information of the 240 who registered for the gathering. Instead of a scattered program, technical papers were grouped together in organized symposiums, where the particular importance of each report was enhanced by presentation in context. Despite the heavy accent on technical papers and informative field trips, those attending the meeting had ample time to enjoy the benefits of a visit to Chicago. The AIME dinner dance was held at the Palmer House, in the Red Lacquer Room. The Chicago Section played host Friday evening at dinner. The MBD held four sessions at the meeting headquarters, the Palmer House, September 4 and 5. Featuring the meetings was a review of taconite concentration and new theories on comminution. The first session opened with a paper on the Structural Features Which Effect the Concentration of Iron Formations, presented by F. J. Tolonen. The paper was centered upon the various members of the low grade iron formations of the separate Michigan districts. The study correlated macrostructure, microstructure, and concentration tests. [ ] Beneficiation Characteristics of Michigan Low Grade Iron Ores, presented by F. X. Tartaron, cochairman of the session, reviewed the work of his laboratory on the beneficiation of low grade ore taken from various strata of a deep shaft on the Marquette Range. The paper included data on flotation, gravity separation, magnetic separation, and combinations of these processes. The economics of low grade ore treatment generated great interest. Ty. Maki offered a compilation and correlation of field results with magnetic separators in ferrosilicon and magnetite medium recovery circuits. Following the morning session, 130 persons attended a luncheon, followed by a brief business meeting. Later, a film illustrating the grinding, separation, and pelletizing steps investigated by the Mines Experiment Bureau, was presented by H. H. Wade. T. E. Ban, and L. J. Erck gave a report on pelletizing which evoked much discussion. R. A. Limons presented a paper on the Mineralogy of Blast Furnace Sinter, for its author, H. M. Kraner. Friday sessions featured a new hypothesis for high speed drill rod milling and a new technical approach to comminution. Jack Myers commented that Consolidated's large rod mill was a hammer mill turned inside out. Steve Erickson described the use of Cyclones for Heavy Media Concentration of Iron Ore Fines. Bob Meaders gave a Progress Report on the Aerofall Mill. Shiou-Chuan Sun described an improved high frequency analyzer for studying the conductivity of suspensions of various minerals. L. A. Roe discussed a magnetic reflux condensor which enabled him to determine the degree of liberation of magnetic iron ores. Roy A. Johnson described a function of the hydroscilator in which the fan rake was eliminated in favor of a conical bottom. The Industrial Minerals Division sessions held September 5 and 6 and were well attended. The Friday morning session was particularly concerned with developments and advances in industrial minerals with special emphasis on the Chicago area. The first two papers dealt with transportation on the Great Lakes and fuel movement into the Chicago area. The third paper proved to be of great interest, turning the spotlight on the fairly new hydraulic mining methods introduced by a silica company in the Ottawa, Ill. field.

Jan 1, 1952

By A. J. May

THE Star shaft is near the north boundary of the group of mining claims belonging to the Ground Hog Unit of the American Smelting and Refining Co., near Vanadium, N. Mex. The shaft bins and surface plant are served by a siding from the Atchison, Topeka and Santa Fe railroad, and this factor of railroad transportation influenced the choice of site. This paper describes the shaft sinking only, and does not cover the surface plant or other parts of the mine or its equipment. Experience with this shaft seems of interest because of the mechanical mucking, good rate of progress, and the costs obtained at the present level of labor and material costs. The shaft has four compartments, as shown in fig. 1. Equipment: Riddell Mucker: The mucking was done by a clamshell bucket and a Riddell mucker, which, as in other shafts sunk with this machine, consisted of a carriage mounted on axles with double flanged wheels that traveled back and forth on a swinging track, parallel to the long axis of the shaft (fig. 2 to 6). Three air motors were mounted on the carriage; one hoisted the clam, one operated the bucket opening and closing device, and the third moved the carriage along the track. The carriage was designed with guide shoes and could be hoisted to the surface in either skip compartment without trouble (fig. 4). During blasting operations the clam was tied on the rails and the carriage was hoisted up a few sets to protect it from flying rock. No attempt was made to hoist the carriage and clam together lest the clam catch in the timbers. The track on which the carriage operated was built of extra heavy 6 in. pipe with 1x2 in. strap welded on top for rails. A 1/2x4 in. angle was welded on the bottom of the 6 in. pipe with a 1 in. round rod welded in the angle for a filler and additional strength. The end or cross pieces of the track which kept the track to gauge, were also made of reinforced, heavy 6 in. pipe and were bolted to the long members on which the carriage traveled (fig. 2 and 3). This section of track was used, instead of heavy railroad rails, for two reasons: (1) this section would bend before it snapped and was much safer for the men in the bottom; and (2) it was a better blasting shield, and protected the timbers better, in fact, only five wall plates were broken by blasting in 1926 ft of shaft, although 150 to 225 lb of 40 pct powder was loaded per round, depending on the ground conditions. The swinging track was supported by four 5/s in. hoisting cables anchored to the end plates. There were also four safety cables fastened two to three sets above the carriage, which would catch the carriage if one of the supporting cables should fail for any reason (fig. 7). Clamshell Buckets: Two clams were used, each of 3/s yard capacity, both manufactured by Blaw Knox, Nos. 662 and 663. The No. 663 clam was 4 in. wider and 5 in. shorter than the No. 662, but seemed to dig and load more satisfactorily. It was easier to hoist and lower when it came up for repair. It did not turn over as easily, had less spill

Jan 1, 1950

By Dean Goodermote, Carla S. Stone

I Introduction Coal fuels China. Roughly 70 percent of all commercial energy demand is supplied by domestic coal production and with the recent Chinese opening to the West, the Chinese Coal Industry may figure prominently in the export market as well. Because of the importance of China's coal industry to the future of China and the Pacific Rim energy balance, this paper reviews the industry and offers some cautious projections for its outlook. II Energy's Position in the Current Political and Economic Climate Traditionally, Chinese society has been dominated by the policies of its most important government leaders. Deng Xiaoping, Vice Chairman of the Communist Party is the current leader of China. Deng and his proteges are pragmatists. Although China's government structure is based on Marxist/Leninist tradition, Deng and his followers are promoting experiments with market economics and expanded relationships with Western Countries, which have encouraged foreign investment in China. Energy companies represent just one type of industry that is interested in helping the Chinese to develop their abundant natural resources. Although China's leadership is committed to a program of economic modernization, that program currently is experiencing what the Chinese government terms "readjustment". Readjustment cuts back in imports due to deficient foreign exchange and deemphasizes heavy industry, while it encourages agricultural and consumer goods output and, most imporant, energy production. Increased Chinese coal and oil production is essential both to fuel industry and, equally important, to provide foreign exchange. If sufficient energy production is not forthcoming, then economic growth will be severely retarded. China's 1979 per capita GNP of $260 is only slightly better than the weighted average achieved by low income countries of $230. (1) Delays in growth could lead to social unrest, threatening the position of the current leadership. Since there is no institutionalized mechanism for leadership succession and policy continuation, it is reasonable to assume that leadership changes could result in energy policy changes. III Energy Consumption Energy production is important to China's future economic health as highlighted by the World Bank. If China's economy grows rapidly, 5 percent to 6 percent during this decade, the Bank noted, a significant energy shortfall could occur as early as 1985. This state of affairs contrasts sharply with China's current position as a net hydrocarbon exporter. (2) To assure a healthy economic future, China's leadership is attempting to reduce its rate of increase in energy demand through conservation as well as to boost energy output. A massive conservation promotion program has been underway since 1979 and there is much room for improvement. China's industrial sector is only about half as energy efficient as is U.S. industry. (3) During the last two decades, each percent of increase in GNP has been accompanied by a 1.8 percent of increase in energy consumption. (4) This compares rather poorly with the United States where a less than one-to-one relationship exists. IV Energy Supply The short term prospects for oil production are uncertain. Production increases were rapid in the 1960's and early 1970's, averaging 20 percent annually, but most of this increase came from one field, Daquing. Now that Daquing's production has peaked and the offshore potential has yet to be developed, petroleum production has maintained a plateau of 2.1 million b/d, at least temporarily, of which approximately 15 percent is exported. (5) Output

Jan 1, 1982

By D. J. Pye

Certain high molecular weight synthetic polymers in very dilute solutions decrease water mobility in porous media 5 to 20 times more than would be expected from the solution viscosity. This indicates that increasing water viscosity to reduce adverse mobility ratios in water floods is economically feasible in many situations. Laboratory results are consistent with accepted theory with respect to improved areal sweep, permeability distribution and displacement efficiencies as would be predicted from the solution mobility measured in the core. The laboratory results have been confirmed by field pilot floods which recovered 80 per cent and 100 per cent more oil than comparative water-flood pilots in fields containing 16 cp and 130 cp oil respectively. Economic analyses based on pilot data indicate the method to be profitable. INTRODUCTION The desirability of improving the water-oil mobility ratio in waterflood-ing operations has long been appreciated, especially for high viscosity crudes. Methods of reducing the oil viscosity by application of heat, gas resaturation and miscible drives have met with some success. Conversely, it has been generally conceded that increasing the water viscosity would also be effective, but the amount of thickening agent required to effect an appreciable increase in viscosity is discouragingly high. The use of such materials as glycerin, sugar, or glycols is completely out of the question economically, so that considerable attention has been given to the use of the much more efficient synthetic water-soluble polymers as viscosity improvers; but even these materials are not economically attractive. If increased water viscosity could be economically realized, marked improvements in areal sweep efficiency, as discussed by Caudle and Wittel and others, would be realized in field operations. Similarly, the improved mobility ratio would bring about increased recoveries by correcting permeability distribution problems as discussed by Stiles2 and Dykstra and Parsons,' and improvements in displacement efficiency would be obtained as recognized by Buckley and Leverett4 and Welge.5 LABORATORY STUDIES THE RESISTANCE EFFECT In the course of research to develop a more efficient water-soluble polymer viscosity builder, we discovered that a very few types of water-soluble polymers exhibited a most unusual and very interesting property not previously observed. Among the earliest materials showing such activity were polymers containing acry-lamide. Fig. 1 shows a typical plot of the solution viscosity vs concentration for one of these polymer solutions as determined in an Ostwald viscometer. As usual, such a plot is an approximate straight line on semi-logarithmic paper. Now, an inspection of Darcy's law, shows that a viscosity value can also be determined in a formation sample if the pressure, flow rate and permeability are known. If the core permeability is previously determined with wa- ter or brine, then the viscosity of another aqueous fluid may be determined from the equation. The viscosities so determined for glycerin (glycol or polyvinyl alcohol solutions, for example) agree with the viscometer determinations. However, in the case of the water-soluble polymer solutions in which we are interested, the viscosities measured in the formation sample depart very markedly from the viscometer values. A typical relationship for a polymer solution is also shown in Fig. 1. This unusual departure from the expected response is referred to as a resistance property of the polymer and is quantified as "resistance factor". Since the resistance factor R can best be determined in a core under study, the term has been defined on the basis of the ratio of the brine mobility to the polymer solution mobility at residual oil saturation so that:

Jan 1, 1965

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.' Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.'-' At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,' but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By Nicholas J. Grant, Rolf Nordheim, Bill C. Gissen

The system Cb-Re was examined in detail utilizing pure metals, careful melting techniques, and heat treatments. Metallographic and X-my methods were utilized for phase identification. In addition to soli-dus determinations, the composition limits and mode of formation of the intermetallic compounds 0 and X were determined. The binary constitution diagram Cb-Re has been the subject of a number of investigations.'-7 Two intermetallic phases have been described and tentative diagrams have been proposed. It was the aim of this investigation to obtain a complete and more accurate diagram through the use of purer alloys and improved techniques. The diagram worked out by Knapton7 was published after our experiments were concluded. EXPERIMENTAL METHODS The starting materials were Re powder of 99.95 pct purity, supplied by the Chase Brass and Copper Co., and Cb rondelles of 99.6 pct purity, supplied by the Electro Metallurgical Co. Typical analyses are given in Table I. The alloys were prepared from compacted Re powder and Cb rondelles; for critical compositions master alloys were used. The melts varied from 5 to 50 g and were melted nonconsumably in an Heraeus arc furnace, under ti-tanium-gettered laboratory grade argon. It was necessary to invert the buttons and remelt, followed by crushing and further remeltings, the number of which depended on the nature of the fracture of the alloy. The weight of each alloy was carefully checked after each melting operation. It was found that significant weight losses occurred only when loose Re powder was used. These losses amounted to a maximum of 3 wt pct in such instances, but did not occur after the charge was once molten, regardless of the composition. Typical loss of weight after 4 remelts, including crushing, amounted to 0.2 wt pct. Oxygen pickup during successive melting cycles did not appear to be significant, since the weight gain values never exceeded 0.01 wt pct. Control of the composition of the alloys was not too difficult; however, the problem of homogenization was a far greater one. Optimum alloying conditions were finally achieved by a combination of master alloy production and repeated crushing and remelting cycles. The compositions of the alloys utilized to determine the constitution diagram are listed in Table 11. The weight balance method was used ultimately as the sole analytical method, since repeated checks indicated that it was accurate to 0.2 pct, if the weight losses were small. The results were double-checked by a metallographic study of the homogeneity of the samples, since this was presumed to be the more serious factor. Heat treatments at 1200°C or lower were accomplished by sealing the specimens in Vycor tubes, heating in a Globar furnace, followed by air cooling. This was considered to be an adequate quench because of the very low temperatures involved. For temperatures of 1200" to 1900°, alloys were homogenized and heat treated in a tungsten-filament resistance vacuum furnace. From 1900" to 2750" a tantalum-tube resistance furnace was utilized, operating under a vacuum of 105 mm Hg. The temperature measurements up to 1200" were made by means of platinum-platinum 10 pct Rh thermocouples, with an accuracy of 5°C. For temperature measurements greater than 1200°C, optical pyrometers were used. They were calibrated against a standardized instru-

Jan 1, 1962

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By C. A. Hartinagel

During 1941, the total production of crude oil in New York state was 5,185,000 bbl. This represents a small increase over the average for the past five years. From 1921, when the annual production of the state amounted to only 988,000 bbl., there was a regular annual increase in production (excepting one or two years) until the 5,000,000-bbl. mark was reached in 1937, After more than 20 years of oil recovery by flooding methods, it was generally believed, until a few months ago, that the rate of production was nearly at its peak and within a few years the fields would experience a gradual decline as the thicker sands became exhausted and the thinner ones could be worked only at increasing costs. As a result of the present emergency, however, unusual efforts are being made, in spite of higher costs of operation, to increase the output of Pennsylvania grade oil, to which the New York product belongs. Since most of any increased production would be obtained by flooding, and since floods travel slowly, no large increase in production can be expected for some months to come. During the first year, 10 or 15 per cent increase could be obtained, but maximum production, an increase of perhaps 40 per cent, could not be expected until some time during the second or third year. In the Allegany fields, which account for two thirds of the state's oil production, 1246 wells, including water-intake wells, were drilled during the year; 390 more than in the preceding year and 590 more than in 1939. It is evident that much of the best oil territory has already been developed. As producers move toward edge properties and thinner sands, returns will be smaller, whereas costs remain the same or, under war conditions, become higher. It is estimated that at least 60 million barrels of oil is in sight and will be produced from the thicker sands by present recovery methods. In the thinner sands and edge properties, some 35 million additional barrels can be produced at a profit only if prices become higher. In view of the fact that there is little hope of finding new oil pools in New York, one of the future problems of the oil producer will be to obtain adequate returns for increased production costs. The year started with a posted price of $2.15 per barrel of crude. There were five successive price increases until the high of the year was reached at $2.98 on Aug. 14. Eight days later the Office of Price Administration directed that the price be reduced to the June level of $2.75 a barrel, which remained in effect to the end of the year. With rising costs of operation, it is feared that many of the smaller properties cannot continue production unless the Federal price cut is revoked. During the year, Allegany Refiners Inc., a local enterprise founded in 1933, with plant at Bolivar, western Allegany County, increased its refining capacity from 1000 to 1500 bbl. daily. At the same time equipment was added to make the plant a complete lubricating-oil refinery, including facilities for the refining of wax into the finished product. Previous to the enlargement, it was necessary to sell the wax

Jan 1, 1942

By Sven Fornander

An account is given of the way in which a new process for desulphurization of hot metal is carried out at a Swedish blastfurnace plant. In the process powdered burnt lime is used as a desulphurizing agent in a rotary furnace. Results are given. IN a paper by Kalling et al.* the fundamentals of a new process for desulphurization of hot metal using powdered burnt lime as a desulphurizing agent were outlined. The purpose of the present paper is to give a brief account of the way in which this process is being carried out in practice by Surahammars Bruks AB, Sweden, and of the results obtained. + The hot metal from the blast furnace is tapped into a ladle of 15 tons capacity and transferred to a rotary furnace, a simplified drawing of which is given in Fig. 1. The rotary furnace has a total length of about 160 in. and an outside diameter of the rings of about 130 in. The furnace is in a horizontal position, with its rings placed on four rollers, and can be rotated by a driving mechanism at various speeds of up to 34 rpm. The rotary furnace and its driving mechanism were designed and constructed at Surahammar. The hot metal is charged into the rotary furnace through the opening to the left in Fig. 1. See Fig. 2. An addition is then made to the furnace consisting of finely ground burnt lime amounting to 2 pct of the weight of the hot metal as well as 0.5 pct of coke breeze. After the additions are made, the furnace is sealed to the atmosphere by means of two lids and set in rotary motion at a rate of 34 rpm. The sulphur in the hot metal is rapidly absorbed by the lime added, the time of treatment needed is normally 30 min. The process is then stopped, the lid is removed, and the furnace is lifted up by a crane and used as a tilting ladle for pouring the metal into the pig-iron molds, Fig. 3. Process Metallurgy The hot metal charged into the rotary furnace has a composition which usually lies within the following limits: C, 3.70 to 4.10 pct; Si, 0.80 to 1.80; Mn, 0.40 to 0.80; P, 0.025 to 0.030; and S, 0.060 to 0.200. Figs. 4 and 5 give examples of the changes in hot metal composition taking place during the treatment in the rotary furnace. As will be seen from the diagrams, the sulphur content of the metal decreases very rapidly during the first 10 min of treatment from about 0.100 to about 0.020 pct S. During the following 20 min, the sulphur content goes down slowly to about 0.005 pct S. The carbon and silicon contents of the metal decrease by about 0.10 pct each during the treatment. The manganese and phosphorus contents remain unchanged. Thus, if the process is started with an iron of the composition given above, the finishing composition of the metal usually lies within the following limits: C, 3.60 to 4.00 pct; Si, 0.70 to 1.70; Mn, 0.40 to 0.80; P, 0.025 to 0.030; and S, 0.002 to 0.020. The chemical reaction taking place during the process can be written:

Jan 1, 1952

By F. M. Lewis, E. C. Johnson

Used as a classifier in a plant expanding capacity or changing to closed-circuit operation, the liquid-solid cyclone offers the advantage of being adaptable to existing conditions. This paper presents the costs involved and experience gained from operating a unit of this kind. BY now application of the liquid-solid cyclone to various classification problems in the chemical and metallurgical fields is more or less familiar. A less publicized application receiving wider consideration as time goes on is its use as a classifier in closed-circuit grinding operations. This paper presents the costs involved and the experience gained from operating a unit of this kind. In May 1951 the Tennessee Copper Co. installed in its London mill at Copperhill, Tenn., a liquid-solid cyclone in closed circuit with a 6x12-ft ball mill. The circuit in which this cyclone is used is the regrind or secondary grinding circuit of a copper flotation plant. Originally it consisted of a 7x1-ft conical ball mill in closed circuit with a bowl classifier. Changes made in the primary grinding circuit of the mill necessitated a regrind circuit of greater capacity. The bulk concentrate to be ground was raised from 900 or 1000 tpd to 1200 or 1300 tpd, and to accommodate this increase a 6x12-ft ball mill which had been in the primary grinding circuit was moved into the regrind circuit. When this was done it was found that the classifier was too small to give efficient operation. Space in the plant was at a premium, and since use of the cyclone offered considerable economy the installation shown in Figs. 1-3 was made. The unit installed is a 24-in. diam cyclone classifier with a 20" cone angle. Diameter of the vortex finder is 8 in., the feed entrance area 20 sq. in. Maximum diameter of the adjustable apex valve is 6 in. and minimum diameter approximately 3.5 in. To refer again to Figs. 1 and 2, the cyclone* is mounted motor. It is charged with 18 tons of 1-in. balls. The overflow, or fines, passes by gravity directly to the copper flotation plant. The ball mill discharge and the new feed combine in a sump from which they are sent to the cone by an 8x6 SRL pump at a rate of 497 gpm. Pressure at the cyclone is 5 psi. For reasons dictated by the nature of the ore treated, particularly the bonding of fine grains of chalcopyrite to pyrrhotite, the froth from the second cell of the copper rougher circuit is returned to the regrind mill. This flow, which somewhat complicates the standard closed-circuit calculation, is seen in Fig. 1 to be 156 tpd of solids. This combines with the cyclone classifier underflow to constitute the ball mill feed. The requirement of the regrind product is that it be 77 to 80 pct —200 mesh. The liquid-solids cyclone operating in conjunction with the 6x12-ft mill adequately met this requirement. Of primary importance is the fact that this arrangement provided sufficient classification capacity to replace the undersized classifier and was capable of building up a circulating load to 87 pct, large enough to give an efficient grind. In this instance the circulating load is taken as the ratio of sands to new feed. Any comparison of performance between this liquid-solid cyclone and the replaced classifier would of course be unfair, since the bowl classifier was

Jan 1, 1955

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.' 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 A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By James Kemp

PostScript to a paper presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 129 to 154. The writer looked over the quarry with care in the search for fossils, having in mind shells or corals of fairly large size. In the brilliant summer sunshine, none were observed on the glaring white ledges. The impression was gained that none were present and the statement to this effect was made in the edition of this paper published in the Bulletin' of the Institute for February, 1915, p. 136. On closer examination in the laboratory it has been discovered that the limestone itself is made up of minute organisms, which are clearly revealed by microscopic examination of thin sections. The principal component of the rock is a small foraminifer, 0.1 to 0.3 in. (2.5 to 7 mm.), of the genus Orbitoides, presumably an Oligocenic form. Figs. 1 and 2. illustrate it. The accompanying description has been kindly summarized by Marjorie O'Connell, M. A., Curator in Paleontology in Columbia University, who first detected the evidences of organisms in the rock. Orbitoides kempi O'CONNELL N. SP.1 The foraminiferan which makes up the Seboruco limestone is an Orbitoides of a Species new to North America. The only Orbitoides heretofore described from this country is 0. mantelli from the lower Oligocenic of the Gulf States. This form from Cuba, then, so different in all of its characteristics from the 0. mantelli, is of great interest as perhaps forming a basis of correlation over wide areas. The most closely related Species is 0. dispansa Sowerby, which occurs in the Nummulite limestone of the Eocenic of the Bavarian . Alps, in the Priabona beds of the lower Oligocenic of Massano, and elsewhere in Italy, as described by Gümbel.2 The age of the limestone in Cuba would thus Seem to be of upper Eocenic or lower Oligocenic age, probably the latter. The fossil has the form of a sphere Surrounded by a wavy rim of horizontal extent, the whole resembling two flat-brimmed, round-crowned hats placed base to base. The total extent of the Shell ranges up to 7+ mm., while the thickness of the central sphere is 2.5 mm. in one of the largest individuals. Like all of the other Species of Orbitoides, this form begins with a Single layer of chambers which multiply in one plane and assume a circular outline; but it is in the subsequent growth that the distinguishing specific characters appear, for the chambers at the central portion of the shell increase more rapidly than do those near the periphery and in consequence a Swelling is produced which finally gives the Spherical form which is so characteristic. The rim, on the other hand, shows little chamber-increase and remains thin. This is clearly Shown in the sections figured, where the central row of larger chambers forms the equatorial zone. Radiating from this row, in section, there appear, a number of solid cones alternating with broad reticulated ones. The solid cones mark the more dense structure forming the walls surrounding the reticulated or chambered cones. These appear upon the Surface as distinct pits, whereas the solid part appears as raised walls.

Jan 7, 1915

By Shiou-Chuan Sun

SHIOU-CHUAN SUN (author's reply).-Thanks are extended to Professor Hassialis for his recognition of the usefulness of a new tool, the cataphoretic cell, as an adjunct to the bubble machine and the abstraction test. His questions concerning adsorption, dielectric constant, floatability, activation, and depression are interesting and worthy of discussion. I According to Mueller,28 it is questionable that any of the present formulas gives absolute values of zeta potentials which are completely accurate. The problem is further complicated by the question" of whether the "dielectric constant" has any meaning at all for such a microscopically thin layer. With these in mind, the results in this paper should be considered in the relative sense as a first approximation and not as absolute quantities. Adsorption Referring to item a of Fig. 8, the dielectric constant and the viscosity of the xanthate solutions are the same for galena, sphalerite and quartz. If dielectric constant and viscosity (but not the adsorption) were the first-order variable of the cataphoretic system, as claimed by Professor Hassialis, then the magnitudes of zeta coefficient of galena, spha)erite and quartz would have been similar to each other. These are not. The big difference of zeta coefficient of these three minerals in the same xanthate solutions is not altogether unjustified to be attributed to their difference in adsorption of xanthate ions. This is supported by the results of chemical abstraction tests reported by Ince.14 Again, the big difference of zeta coefficient between wollastonite, calcite, and fluorite in the same laurylamine hydrochloride solutions (p. 118, Figs. 58, 59, and 60 of ref. r5) also indicates that the cataphoretic system is not governed chiefly by the dielectric constant. Beside the data shown in Fig. 8, other experimental evidences15 which support the idea of correlation between adsorption and zeta coefficient are: (I) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of various concentrations of sodium cyanide, (2) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of constant concentration of copper sulphate at different pH values, and (3) there is a qualitative parallelism between zeta coefficient curve and chemical abstraction curve of quartz in solutions with constant concentration of barium chloride at different pH values. The above mentioned experimental results are generally in agreement with Gouy's double layer theory,1-5 and support this idea that the concentration and the kind of ions adsorbed at the mineral surface and in the adjacent surrounding liquid chiefly govern the electrokinetic phenomena. Dielectric constant and viscosity of the liquid medium may be of somewhat lesser importance. It follows that the correlation between the coefficient and adsorption as claimed in this paper is justified. Dielectric Constant The term "dielectric constant " was first introduced into the electrokinetic equations by Perrin.30 In a footnote of his publication he states that Holmheltz has forgotten to include the dielectric constant. The conversion of the moment29 to the zeta potential involves an additional difficulty and confusion not involved for the moment, namely, assigning a value to the dielectric coefficient. This is conventionally assumed to be constant and equal to the dielectric constant of the bulk liquid. 21 The published literature 10, 12 indicates that the values of dielectric constant for dilute chemical solutions have been assumed as those of pure water.

Jan 1, 1947