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By C. Perez-Rosales

A statistical method for determining simultaneously some of the basic geometrical characteristics of porous media such as porsity, specific surface* mean pore width, mean grain thickness and absolute permeability is presented. The proposed method is characterized by its simplicity and the minimum amount of laboratory equipment that it requires. The experimental procedure used to evaluate the various geometrical characteristics is based 'pan the 'surface analysis Of a a In view of this fact the app1icability Of the method is limited to homogeneous and isotropic materials. INTRODUCTION The behavior of a fluid flowing through a porous medium depends, among other things, upon the internal geometry of the medium; hence the importance of developing efficient methods to determine the geometrical properties of porous materials. This paper describes a statistical method to determine simultaneously some of the basic geometrical properties of porous materials such as porosity, specific surface, mean pore width, mean grain thickness and absolute permeability. The mathematical formulation has been developed that the data required to calculate the various geometrical characteristics of a sample can be easily measured by analyzing a section of the sample with an evenly spaced grid. THEORY A simple way of obtaining information about the internal geometry of a porous material is to throw a point at random over a cross-section of a sample. l-Through this procedure the porosity can be detemined.l,2 By considering that the material is homogeneous and isotropic, and that the point is dropped many times, the porosity 4 is given by where N is the total number of times the point is thrown and n is he number of times the point falls within pore areas. Another simple manner of analyzing the structural characteristics of a porous material is to superimpose an arbitrarily long line on a cross-section so that its length is evenly distributed over the surface area. Through this procedure the porosity can also be determined. If L is the total length of the line, and 1 is the sum of the lengths of the line segments within void spaces, the porosity is given by 4 = —.1.............. (2) The advantage of this type of analysis is that geometrical characteristics other than porosity can be obtained. Thus, if c represents the number of intersections between the line and the perimeter of pores, it can be shown3 that the specific surface, defined as he surface area of pores per unit bulk volume, is given by To give a proper description of the internal geometry of a porous medium, it is necessary to define quantities that characterize the notions of pore size and grain size. Unfortunately, because of the complexity of porous materials, it is difficult to give exact geometrical definitions of what is meant by the ConCePtS of "poresl' and "grains", especially when dealing with consolidated materials. Never theless, one often talks about the "size of pores" and the "size of grains" without defining accurately the terms. A possible solution to this problem follows. Assume that an arbitrarily long line is placed on a section of a sample so that the line is evenly distributed over the surface area (see Fig. 1). 1n a system like this, each line segment within a void space will be, by definition, the pore width in a given location and direction. Consequently, if the

Jan 1, 1970

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

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

Jan 1, 1964

By 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&apos;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 A. Rosenzweig, M. M. Karnowsky

The generalized binary diagram of the Au-Sn-Pb system is presented. The chief characteristic is the pseudobinary between lead and AuSn. On the high-gold side of the pseudobinary, four reaction isotherms were found at 363°, 274°, 225°, and 204°C. On the low-gold side of the pseudobinary, three reaction isotherms at 277°, 205°, and 176°C were found. A vertical section from the eutectic solder composition to gold was developed from the isothermal sections generated. METALLURGICAL problems arising from the intentional or accidental formation of Au-Sn-Pb alloys in soldering applications have indicated a need for information on the phase equilibria in this ternary system. The literature indicates that a complete diagram presenting this information has not been prepared. Even the recent excellent work by prince&apos; entitled "The Au-Pb-Sn Ternary System" actually extends only to the AuSn or 50 at. pct Au range. There are more events in the 50 to 100 at. pct Au than in the less than 50 at. pct range. This article by Prince furnished much guidance in preparing this report. Initial efforts with the isopleth from the eutectic solder composition 61.9 wt pct Sn-38.1 wt pct Pb and 0 to 90 wt pct Au indicated that extensions of the work to the whole of the diagram (even if in less detail) were necessary to understand this system. In undertaking the construction of such a diagram, this study used differential thermal analyses (DTA) and metallography with verification and identification of phases by electron microprobe analyses. EXPERIMENTAL PROCEDURE The procedure began with the development of a cell which would be unreactive with lead, tin, and gold, retain its strength to 1100°C, exclude oxygen, and also furnish a suitable well for insertion and protection of a thermocouple to monitor temperature changes in the material. Such a cell would make it possible to reuse the sample should a repetition of determination be desired. Fig. 1 is a photograph of two such quartz cells as finally developed. The specimens have been run many times. The cell is made up of an inner sample bucket and an outer capsule with a thermocouple well which the sample surrounds. The DTA unit was an assembly devised from available instrumentation. The sample holder was a 3-in.-long cylinder of nickel, 2 1/2 in. in diam, fitted securely in a vertical tube furnace. Two holes 7/8 in. in diam were symmetrically located to receive the quartz cells. A dummy cell with nickel powder was used as the reference. The absolute temperature was recorded with a Pt/Pt 10-pct Rh thermocouple with an automatic Kaye ice bath compensator. (Calibration indicated the compensator to be accurate to better than ±0.5° over the 100° to 1000°C range.) The absolute temperature was measured in the sample and recorded on an L&N mul-tirange recorder with a full-scale display of 1 mv and automatic ranging of 99 mv. The differential signal between the sample temperature and the reference temperature was amplified with an L&N microvolt amplifier and recorded on an L&N Speedomax G recorder. Since two charts were obtained, the chart speeds were equalized and each event was noted on the differential chart, and the temperature at that time was obtained from the temperature record.

Jan 1, 1969

By Catherine T. Aimone

Specimens of copper-bearing quartz monzonite were subjected to a plane shock wave simulating high compressional stresses in the proximity of a borehole wall. Fragmentation was studied as a function of stress levels between 1.6 GPa (23 x 104 psi) and 7.3 GPa(105.8x104 psi) and pulse durations ranging from 1.1 µs to 6.9 us. Both explosive pressure and pulse duration were shown to have a strong effect on particle size distribution. While the effect of pressure is well recognized, the effect of pulse duration indicates that ultimate fragmentation increases with the time of application of a plane wave pulse. At high pulse durations, degree of fragmentation is more sensitive to changes in pressure than at low pulse durations.

Jan 1, 1984

By C. R. Kuzell

The Editor desires to call attention to the charts in the paper of the above title which were published in the August Bulletin on pages 2190 and 2191. It was impracticable to include in the Bulletin. charts of sufficient size to be used as working diagrams for the direct determination of operating values, but the Institute is prepared to furnish copies of these charts on a large-size scale, at a moderate cost, to those who desire to have them for this purpose. CORRECTIONS Page 2185, line 3. For "is accessory apparatus" read "in accessory. apparatus." Page 2188. Substitute for lines 11 and 12: Nitrogen, oxygen, carbon monoxide, Cp = 6.50 + 0.0010T Hydrogen, Cp = 6.50 + 0.0009T

Jan 9, 1914

By A. Mitchell, M. Etienne

VARIOUS&apos;-3 reports on the electroslag remelting process refer to the "thin skin of slag" existing around the slag pool and the solidifying ingot, but none considers the various mechanisms by which this layer forms and thus influences the surface quality of the ingot. A vertical section4,5 of the Cao-CaF2-Al2O3 diagram is shown in Fig. 1 between CaF2 and 6Al2.CaO3 From this, it is seen that a typical "70:30" CaF2:A1a3 slag will solidify to produce 6Al2O3.CaO primary phase in a eutectic matrix. The commercial slags contain sufficient CaO to produce* this composition by both the

Jan 1, 1969

By J. L. Huiatt, G. M. Potter, R. B. Tippin

The US Bureau of Mines and Great Salt Lake Minerals and Chemical Corp. have developed a froth flotation process for concentrating potassium salts from Great Salt Lake solar evaporites containing about 6% K2O. The crude evaporites, which were predominately halite (NaCl) with smaller amounts of kainite (KCl.MgS0, 2.7Hp0) and schoenite KeS0,MgS04.6H,0), were conditioned in a saturated brine solution., thus converting nonfloatable kainite to the floatable mineral schoenite. Schoenite was then selectively floated with a medium-molecular-weight fatty acid. Continuous small-scale pilot-plant testing indicated that 80% of the potassium could be recovered from the crude evaporites in flotation concentrates assaying about 13% K2O.

Jan 1, 1976

By M. T. McDonough

THE data relative to the effect of metal depth on slag volume was obtained from the operation on two acid electric furnaces in which heats of various sizes were produced. The furnaces used were of 3 and 5-ton rated capacity; the heats investigated ranged from 6 to 8 tons. Heats of 7 and 8 tons were made in the larger furnace; heats of 6 tons in the smaller one. Bath depths and diameters were measured on the furnaces when cold and each is accurate to one inch. Both the metal charge and the slag were weighed on a track scale accurate to ± 25 lb. All other components added to the furnace were weighed on a wheelbarrow scale accurate to ±5 lb.

Jan 1, 1947

Apr. 26-May 11, Liege International Fair, Liege, Belgium. May 4-8, Electrochemical Society, Inc., Spring meeting, Benjamin Franklin Hotel, Philadelphia. May 5-6, National Air Pollution Symposium, Huntington Hotel, Pasadena. May 5-7, American. Mining Congress, coal convention, Netherland Plaza Hotel, Cincinnati. May 6-9, Scientific Apparatus Makers Assn., annual meeting, Edgewater Beach Hotel, Chicago. May 9-10, AIME, joint meeting, Industrial Minerals Div. and Metals Branch, Davenport Hotel, Spokane, Wash. May 11-14, American Institute of Chemical Engineers, Atlanta Biltmore Hotel, Atlanta. May 17, AIME, Chicago Section, President&apos;s night dinner dance, Shoreland Hotel, Chicago. May 27, AIME, Morenci Subsection, Longfellow Inn, Morenci, Ariz. June 2-4, Chemical Institute of Canada, annual conference, Montreal. June 4-14, Mechanical Handling Exhibition and Convention, Olympia, London.

Jan 1, 1952

Jan 1, 1920

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10&apos; to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By HORACE V. WlNCHELL

Location. THE St. Helens mining-district, indicated in sketch-map, Fig. 1, is chiefly in Townships 9 and 10 North, Ranges 5 and 6 East, of the Willamette meridian, in Skamania county, Wash. There is no railroad or even a wagon-road at present connecting it with any base of supplies; access is usually by wagon-road for FIG. I.-SKETCH-MAP OF THE STATE OF WASHINGTON. about 50 miles from the town of Castle Rock to Spirit lake, and from that point by pony-trail from 6 to 10 miles farther. History. Nearly 20 years ago two German farmers, totally inexperienced in prospecting, penetrated this region upon a hunting and fishing-trip. Their attention was drawn to numerous joints and crevices filled with black, glistening tourmaline, and con-

Oct 1, 1912

By Cyril Stanley Smith

IsolatEd alloys of copper and silicon were prepared and examined by chemical methods more than one hundred years ago, but it was not until the work of Rudolfi l that the equilibrium relations were studied. The early history of the alloys was well described by Baradue-Muller 2 and need not be further discussed here. The diagram of Rudolfi, based entirely on thermal observations, showed sillcon to be soluble in copper up to 4.5 per cent. at 849" C., at which temperature there was a peritectic horizontal resulting from the formation of a ß phase with about 7.4 per cent. silicon from a and liquid with 7.85 per cent. silicon. The ß phase was believed to form a eutectic with Cu3Si at 820" C. and 9.8 per

Jan 1, 1929

By Cyril Stanley Smith

IsolatEd alloys of copper and silicon were prepared and examined by chemical methods more than one hundred years ago, but it was not until the work of Rudolfi l that the equilibrium relations were studied. The early history of the alloys was well described by Baradue-Muller 2 and need not be further discussed here. The diagram of Rudolfi, based entirely on thermal observations, showed sillcon to be soluble in copper up to 4.5 per cent. at 849" C., at which temperature there was a peritectic horizontal resulting from the formation of a ß phase with about 7.4 per cent. silicon from a and liquid with 7.85 per cent. silicon. The ß phase was believed to form a eutectic with Cu3Si at 820" C. and 9.8 per

Jan 1, 1929

NEW MEMBERS The following list comprises the names of those persons who became members during the period of May 10, 1917, to June 10, 1917. ANDERSON, JAMES P.,-Mgr. of the Mines of the Ringwood Co., 50 Church St:, New York, N. Y. BAKER; THOMAS C., Mine Supt., Cia. Santa Gertrudis, S. A. Pachuca, Hidalgo, Mexico. - BARCUS, W. J.. E., Min. Engr., Mining and Metallurgical Dept., General Chemical Co., 25 Broad St., New York,. N. Y. . BENNETT, GEORGE N.,.Min. Engr., Butte & Superior Mining Co., 616 West Gold St., Butte, Mont. BROCKMANN, GUILLERMO, Banker, Gmo. Brockmann & Co., Room 3115, 120 Broadway, New York, N. Y. BROWN, CLYDE L Mining, Box 703, Goldfield, Nev. BRUNSKOG, CARL W., Draftsman, Consolidated Arizona Smelting Co., Humboldt, Ariz. BURRELL,. OSSIAN C Mgr., American Zinc Co. of Tenn., Mascot, Tenn.

Jan 7, 1917

NEW MEMBERS. The following list comprises the names of those persons who became members during the month of June, 1913: Members. ANGERER, VICTOR, Vice-Prest. and Genl. Mgr., Wm. Wharton, Jr. & Co., Inc., 25th St. and Washington Ave., Philadelphia, Pa. BULLOCK, ALLYN, Min. Engr Hazleton, Pa. CUNNINGHAM, NOEL, Met. Engr., Hollinger Gold Mines, Ltd., Timmins, Ont., Canada. ESTABROOK, EDWARD L., Supt. of Colliery 436 Center St., Ashland, Pa. GATES, A. 0., Instructor Purdue Univ., La Fayette, Ind. LUDLUM, ALBERT C., Prest., New York Engrg. Co., 2 Rector St., New York, N. Y. MILLER, HERBERT F., Met. Engr P. 0. Box 142, Verona, Pa MORTON, ELMER T., Min. Engr Clifton, Ariz. MURFIT, RICHARD H.. Fdv. Asst Hess Steel Castings Co., Bridgeton, N. J. QUAYLE, THEODORE W., Chief Sampler, Metcalf Mines, Arizona Copper Co., Metcalf, Ariz.

Jan 7, 1913

By J. Jay Jacobsen

A dynamic regional coal development model is constructed for the Eastern Powder River Basin of Wyoming. Using this model, alternative development schedules from a recent environmental impact statement submitted to the Department of the Interior are simulated (Ref. 1). These alternatives include different mixes of export capacity, different coal conversion techniques within the region, as well as various levels of coal production. Exportation of 70 to 80 percent of an ultimate coal production of 180 million tons (163.3 x l09 kg) per year and the careful phasing of additional public services with population growth effectively reduce the social and environmental impacts of coal development. The alternative involving the addition of 43,000 megawatts of electrical generation capacity has very significant adverse social and environmental impacts on the region.

Jan 1, 1977

By L. Eaton, A. W. Last, J. L. Stevens

COPPER ore from Kennecott Copper&apos;s Ray mine, about 60 miles southeast of Phoenix, Ariz., is concentrated at the company&apos;s mill at Hayden, some 18 miles south of the mine. The Hayden mill is currently treating 16,000 tons of ore per day by flotation, using raconite, a crude butyl xanthate, as a collector for the sulfide copper minerals and lime as a pyrite depressant.1 The ore contains significant amounts of nonsulfide copper minerals, but recovery of these values has been low. The Hayden mill is now being modified to provide for treatment of future ores by leach- precipitation-flotation (L-P-F). This modification, costing about $5 million, is expected to reduce the loss of nonsulfide copper values and improve overall copper recovery by an additional 2 lb per ton of ore.

Jan 11, 1957

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky&apos;s approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky&apos;s approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963