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By D. A. Dahlstrom

(A. C. Richardson and Charles C. Boley, presiding) W. E. BROWN*—In the operation of the cyclone, what factors have you found that will affect its results as far as efficiency goes; for example, if you have coming through the cyclone a pulp of 20 gpm, that has, say, 25 or 30 pct solids, and then from operational characteristics this pulp changes to 35 pct solids but it is still maintaining the same ratio of flow. HOW does that affect the cyclone;) D. A. DAHLSTHOM (author's reply) —It has a definite effect, as you know from Mr. Sutherland's paper,l3 in that as you increase the solid concerltration of your inlet slurry, you will naturally have an according effect on the overflow concell-

Jan 1, 1950

US 4,192,852-Precipitation of iron values as a jarosite from a sulfate solution obtained as a byproduct in the hydrometallurgical processing of zinc sulfide ore The solution is cooled, partially neutralized, and clarified. The clarified solution is heated to a temperature of 80 to 100°C in the presence of sodium, potassium, or ammonium ions to precipitate substantially all of the ferric iron as jarosite The precipitate is thickened, filtered, and washed The residual solution may be processed for zinc or other nonferrous metal values R V. Pammenter and C J Haigh, assigned to Electrolytic Zinc Co of Australasia Ltd. Mar. 11, 1980. 16 pp. (423-42) Filed: 5-8-78 (903,524). Priority- Australia, 5-9-77 (PD0030) (Drawings below.)

Jan 1, 1982

By W. M. Robertson

The rate of crack Propagation thvough a solid meta1 in the presence of a liquid metal has been calculated. The crack is assumed to propagate by solution of the solid in the liquid under the influence of an applied stress, with volume diffusion of the dissolved solute through the liquid controlling the propagation. The calculated velocities can be tens of centimeters per second or higher. THE embrittlement of normally ductile solid metals by liquid metals has been the subject of extensive study, as summarized in the book by Rostoker, McCaughey, and arkuus.' In experimental studies of liquid-metal embrittlement it is usually concluded that the observed crack-propagation rates are too high to be accounted for by diffusion processes. Diffusion is considered to be an unimportant factor and various other mechanisms are invoked to account for the experimental observations. The similarities of liquid-metal embrittlement to stress-corrosion cracking, to hydrogen embrittlement of steel, and to low-temperature embrittlement of bcc metals are frequently used as analogies for these mechanisms.1"3 The present paper assesses how rapidly a crack could propagate by a mechanism of volume diffusion through the liquid metal. We assume that the crack propagates by solution of the solid in the liquid at the crack tip under the influence of the applied stress and diffusion of the dissolved solute away from the crack tip. The model uses only macroscopic thermodynamic, kinetic, and elastic concepts. The calculations indicate that this dissolution-diffusion mechanism can give high crack velocities. In some previous treatments4'' of crack propagation in a liquid-metal environment the fundamental step has been the breaking of atomic bonds at the crack tip. The liquid greatly decreases the energy necessary to break these bonds. The present model assumes the crack is filled with liquid metal; the presence of the liquid is essential because diffusion through the liquid is assumed to control the rate of propagation. With proper modification this model could also apply to stress corrosion in a liquid environment. THEORY Consider a crack in a homogeneous elastic continuum, ignoring all the structural details of the solid. This neglects a host of metallurgical details which can be significant in the problem of liquid-metal embrittlement;' but this simple assumption is a useful approach in evaluating the role of diffusion through the liquid. The stress distribution around the crack tip establishes a gradient in the chemical potential at the tip, which causes a diffusion flux through the liquid away from the tip. The solid-liquid interfacial tension works against crack propagation, since propagation requires creation of interfacial area. From these two considerations we derive the diffusion flux, which then yields an expression for the velocity of the crack tip. The concentration of the solute in the liquid, C, is equal to the equilibrium concentration in the presence of an unstressed, flat surface, Co, plus the excess concentration due to the stress, AC(a), plus the excess concentration due to capillarity, AC(y): We calculate AC(o) and AC(y) and then obtain the diffusion flux. Consider (Fig. 1) a long flat crack of length 2L, thickness 2r, and tip radius r, where r remains constant as the crack propagates in the positive x direction. There is no stress ay in the y direction across the flat surfaces of the crack. The magnitude of the stress at the crack tip due to the applied stress, a,, is given by the relation6 ^=^[l-2^] 12] which, for long narrow cracks, becomes The stress increases the chemical potential in proportion to the strain energy.? The excess chemical potential due to the stress, Ap(a), is given by where 52 is the atomic volume of the solid and E the Young's modulus. Inserting Eq. [3] gives Now consider the crack to be filled with a liquid metal. The excess solubility due to stress, hC(a), is given by the excess chemical potential due to capillarity, Ap(y), is given by8 where y is the solid-liquid interfacial energy, and v1 and YZ are the two principal radii of curvature of any surface point. At the crack tip, r1 = -r and vz = m, so TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME

Jan 1, 1967

By M. E. Wadswort, A. S. Peck

Infrared data disclose that phenacite reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. The absorption band characteristic of the antisymmetrical C = 0 oleate structure appears at a spectral wavelength of 1623 cm-'. Chemisorption also results in the displacement of OH- and silicate from the mineral surface. Infrared absorbance at 1623 cm-1 is correlated with float-ability at different pH for -60-mesh phenacite particles. Phenacite, Be2SiO4, is an ore mineral often associated with quartz, microcline, and chrysoberyl in pegmatites and mica schist. Experimental phenacite beneficiating processes have been confined principally to the flotation of low grade ores occur-ing in several mountain ranges of Utah and Nevada. The U.S. Bureau of Mines ' has recently reported on the separation of phenacite from ore deposits of Mount Wheeler, Nev. Infrared techniques were previously applied by the authors to characterize the role of sodium oleate and oleic acid in the flotation of several non-sulfide minerals.23 A parallel study was projected to the flotation of the orthosilicate mineral phenacite with oleic acid. Infrared spectra provided a 'molecular fingerprint' of the mineral surface and permitted identification of the reaction mechanisms. Infrared data were complemented with flotation and chemical tests. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation, for which data are presented in graphical or spectral form, are described in chronological test order. Phenacite crystals from Mt. Antero, Colo., were obtained from Ward's Co., Monterey, Calif. The crystals were fragmented in a porcelain mortar to -60 mesh and then pretreated with 0.5 molar HC1 for 15 min to remove iron. Then, the mineral particles were washed free of acid with distilled water and dried. Part of the dried material was ground to a fine powder with a Fisher Grinder using an agate mortar and pestle. Next, the powder was placed in a graduated cylinder and mixed with 500 ml of distilled water. The mineral in suspension was decanted from the settled fraction after 5 min, and the colloidal suspension was used for adsorption tests in which a high specific mineral surface area was required for adsorption and infrared analysis. Conditioning was performed in 50 ml glass centrifuge tubes for both infrared and flotation test determinations. Twenty ml of colloidal suspension was used for the infrared adsorption tests. One and a half g of deslimed -60-mesh HCl pretreated phenacite was added to 20 ml of distilled water for flotation conditioning tests. Six mg of oleic acid was used for each infrared adsorption test, and 0.2 mg of oleic acid was used for the flotation conditioning tests. HCl and NaOH were used for pH modification. The pulps were stirred at a speed of about 1500 rpm for 3 min. Then, the solids were separated out and either dried at 50°C or immediately transferred to a float cell. The pH of the residual liquid was determined with a Beckman Zeromatic pH meter. The flotation procedure is described as follows: 1) A 325-1111 glass micro-float cell was filled with distilled water. 2) Conditioned mineral was placed in the cell and the pulp was aerated through the glass fritted bottom at 7 psi pressure. 3) Floated mineral was skimmed from the cell with a glass slide until flotation ceased. (The end point was reached in all tests in less than 2 min.) 4) The flotation products were dried, weighed, and the recovery was calculated. Samples for infrared analysis were made into mulls using either oleic acid or series 13-21 Halocarbon oil obtained from Halocarbon Products Corp., Hacken-sack, N.J. The mulls were placed between two sodium chloride windows. A characteristic phenacite infrared band at 1868 cm-' was used as an internal standard for quantitative determinations in which absorbance at this position was quantified by the baseline-tangent method4 and related to absorbance at 1623 cm-'. The ratio obtained by dividing absorbance at 1623 cm-' by absorbance at 1868 cm-' was defined as an absorbance quotient for use in graphical presentation.

Jan 1, 1968

New York Holds monthly meetings, except June, July and August JOHN A CHURCH, JR, Chairman JOSEPH E POGUE, Vice-chairman SIDNEY ROLLF, Vice-chairman EDWARD C MEAGHER Secretary, Texas Gulf Sulphur Co, 41 E 42nd St, New York M H MERRISS, Treasurer, 42 Broadway, New York ARTHUR NOTMAN T T READ Boston Meets first Monday of each winter month EDWARD C GEITHER, Chairman WILLIAMS BLACK, Vice-chairman DONALD H MCLAUGHLIN, Secretary-treasurer, Rotch Bldg, Harvard Univ, Cambridge, Mass J L GILLSON A G WAITD

Jan 1, 1923

PROF RICHARD ÅKERMAN Stockholm, Sweden PROF RICHARD BECK Friberg, Germany ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HOFFER Leoben, Austria PROF HENRI LOUIS LE CHATELIER Paris France M FLORIS OSMOND Paris, France ALEXANDRE POURCEL Paris, France JOHN E. STEAD Middlesborugh, England DR. ING H. C. EMIL SCHROEDTER Dusseldorf, Germany JAMES M. SWANK (Associate) Philadelphia, Pa. PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia CHARLES D WALCOT Washingtion D.C.

Jan 1, 1910

Coal Division Mineral Industry Education Division Industrial Minerals Division Minerals Beneficiation Division Mineral Economics Division Mining, Geology and Geophysics Division Council R C Stephenson, Chairman (Ind Min Div), M D Cooper (Coal), H F Yancey (Coal), S D Michaelson (MBD), Will Mitchell, Jr (MBD), J R Van Pelt, Jr (MIED), S S Cole (Ind Min Div), J D Forrester (MGGD), L E Shaffer (MIED), E L Clark (MGGD), C W Merrill (MED), E H Robie, Acting Secretary, 29 West 39 Street, New York 18, New York

Jan 1, 1955

PROF RICHARD ÅKERMAN Stockholm, Sweden DR FRANK DAWSON ADAMS Montreal, Canada ANDREW CARNEGIR New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England HERBERT C. HOOVER Leoben, Austria JAMES FURMAN KEMP New York, N.Y. PROF HENRI LOUIS LE CHATELIER Paris France EZEQUIEL ORDONEZ Mexico City, Mexico ALEXANDRE, POURCEL Paris, France PROF RICHARD H, RICHARDS Boston Mass. JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF TSUNASHIRO WADA Tokyo, Japan CHARLES D WALCOT Washingtion D.C.

Jan 1, 1923

PROF RICHARD ÅKERMAN Stockholm, Sweden DR FRANK DAWSON ADAMS Montreal, Canada PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England HERBERT C. HOOVER Leoben, Austria ROBERT W. HUNT Chicago, ILL JAMES FURMAN KEMP New York, N.Y. PROF HENRI LOUIS LE CHATELIER Paris France EZEQUIEL ORDONEZ Mexico City, Mexico ALEXANDRE, POURCEL Paris, France PROF RICHARD H, RICHARDS Boston Mass. JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF TSUNASHIRO WADA Tokyo, Japan CHARLES D WALCOT Washington D.C.

Jan 1, 1923

[Holds monthly meetings, except June, July and August, J JOHN A. CHURCH, JR., Chairman JOSEPH E. POGUE, Vice-chairman SIDNEY ROLLE, Vice-chairman EDWARD C, MEAGHER, Secretary, Texas Gulf Sulphur Co,, 41 E, 42nd St., New York M, H, MERRISS, Treasurer, 42 Broadway, New York ARTHUR NOTMAN T. T, READ Boston Meets first Monday of each winter month. EDWARD C. GEITHER, Chairman WILLIAM S. BLACK, Vice- chairman DONALD H, MCLAUGHLIN, Secretary, treasurer, Rotch Bldg,, Harvard Univ,, Cambridge, Mass. J, L. GILLISON A. G, WAITE]

Jan 1, 1928

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.' Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.', ' The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates' and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By T. W. Martin, T. J. Crocker, J. M. Goris

The current technology of large rock conveyors is reviewed. Based on this investigation two large rock conveyor concepts have been developed and a test facility investigation designed and fabricated. The USBM will test these concepts along with loading and transfer points for handling mine run rock material up to 1.5 m (4.9 ft) in size. An evaluation of open pit mining systems using large rock conveyors documents substantial cost savings when compared to truck haulage.

Jan 1, 1983

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By R. M. Brick

SEGREGATION can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming. steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-12 per cent Si alloys. The phasial condition implicitly described above-solidification over a range of temperatures with a compositional difference between solid. and liquid-is found in nearly all solid solutions or combinations of solid solutions and eutectics. Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually determinable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be. described first because it is an essential part of the picture. CORING Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus 1, 3, 7 and solidus 2, 5, 8, and where the vertical 1, 4, 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. 1b) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1944

By L. M. Pidgeon

The reactive metals are above manganese on the electromotive series. Their compounds are characterized by large heats of formation and they cannot be reduced from their ores by classical methods. Three general production methods have been used: a) Fused salt electrolysis, b) reduction of a halide by another metal, and c) reduction of the oxide by another metal. Method (a) is highly developed, as in the case of aluminum, (b) in the case of titanium, and (c) has been successful in the case of volatile metals such as magnesium and calcium. It is suggested that future improvements will take place in (a), and particularly in (c), but are rather less likely in the case of (b). THIS year of 1963 is the centennial of the birth of both Charles Hall and of Heroult, the founders of the aluminum industry. Aluminum is the one reactive metal which has reached massive stature in modern industry and perhaps the only such metal to have been produced in any quantity before the turn of the century. It has been joined by others, some on a very modest scale, but all of importance and all of fascinating interest. When invited to give the Fifth Extractive Metallurgy lecture, it seemed appropriate to look back upon the short history of this group to trace the developments which brought extraction methods to their present state and, at great risk, offer opinions as to future trends.

Jan 1, 1963