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CHEMICAL PRECIPITATION U.S. 4,067,789 - Removal of soluble manganous ions from a zinc sulfate solution formed by leaching roasted zinc sulfide ore with spent electrolyte. An excess of ammonium persulfate or like oxidant is added to the leach solution to convert manganese to insoluble, filterable gamma-manganese dioxide, and the precipitate separated from the solution by filtration. L. Harris and A. K. Hanson, Jr., assigned to Newmont Exploration Ltd. Jan. 10, 1978. 11 pp. (204-119). Filed: 5-3-76 (682.442). (Drawing on page 67.)

Jan 1, 1979

By R. R. Vandervoort, W. L. Barmore

Tensile creep experiments were conducted on high-purity, poly cvystalline rhenium from 1500" to 2300°C at stresses from 1500 to I0,OOO psi in a vacuum of 10-a torr. The apparent activation energy for creep was 60 kcal per mole, and the steady-state creep rate varied directly with stress to the 3.4 power. Dislocation substructure that developed during creep was studied by transmission electron microscopy. Possible rate-controlling deformation mechanisms are discussed. The creep behavior of most metals at elevated temperature can be represented by the following equation:&apos;&apos;&apos; t = Cf(s)(^)(s/E)nD [1] where i = steady-state creep rate, C = constant, f(s) = a function involving microstructure, s = applied stress, E = the average elastic modulus at test temperature, n = constant, D = diffusion coefficient According to this well-established relationship, metals with higher elastic moduli and lower diffusion coefficients should have greater creep resistance at the same stress and temperature and equivalent mi-crostructures. While no diffusion data are available, the diffusivity of rhenium should be less than that for most other refractory metals because of its high melting point and hcp crystal structure. The Sherby-Simnad relation for calculating atomic mobility in metallic systems3 predicts that the diffusion coefficient for rhenium is less than that experimentally determined for tungsten4 in the temperature region 1500. to 2200°C. At these temperatures the elastic modulus for tungsten5 is only slightly larger than the extrapolated modulus for rhenium.6 Thus, rhenium is a good possibility for a a high-temperature structural material, but few data on the creep of rhenium have been reported. This investigation was undertaken to study the high-tempera-ture deformation behavior of rhenium in detail. EXPERIMENTAL TECHNIQUES The material used in this study was consolidated from high-purity powder. After cold pressing the powder to a plate a in. thick, the billet was sintered in hydrogen at 2250°C for 24 hr. The plate was reduced to 0.100 in. by cold cross rolling with intermediate anneals at 1650°C for 20 min between passes. The plate was further reduced to 0.060 in. by unidirectional cold rolling with similar heat treatments between passes, and then finally stress-relieved in hydrogen at 1650°C for 30 min. Specimens tested at 1900°C and below were pretest-annealed at 1900°C for 2 50 hr. Specimens tested above 1900°C were pretest-annealed at 2400°C for 5 hr. The impurity content in the "as-received" plate was quite low, table I. Essentially no change in impurity levels was detected in specimens after creep testing. All creep tests and annealing treatments were conducted in a vacuum of 10-8 torr in a test furnace heated by a tungsten mesh element. The load was applied to the specimens through a bellows, and stresses were maintained to ±1 pct of the selected value by periodic corrections for changes in specimen cross-sectional area during creep and for changes in the bellows spring force due to load column extension. One-inch-diameter tungsten force rods were used in the hot zone of the furnace. Deformation at temperature was measured by optically tracking gage marks on the specimen. Temperature was measured by a calibrated optical pyrometer and was determined to ±5"C. Grain sizes were determined by the linear intercept method and specimens were examined in the "as-polished" condition, using polarized light. Specimens annealed at 1900°C had a grain size of 52 ± 5µ , and those annealed at 2400°C had a grain size of 148 * 11 µ. Pieces were cut from the gage section of creep-tested specimens and planed to a thickness of about 0.010 in. by spark discharge machining. Thin foils for viewing by transmission electron microscopy were obtained by electropolishing in a solution of 6:3:1 ethyl alcohol, perchloric acid, and butoxy ethanol, respectively, using the window technique. Bath temperature was —4OoC, and the cell potential was 35 v. The foils were examined in Siemens Elmiskop I, operating at 100 kv. RESULTS AND DISCUSSION In order to analyze the results from creep experiments, Eq. [I] is rewritten in the following form: <=Kf(s)ne-/RT [2] where K = constant, ?// = apparent activation energy for creep,

Jan 1, 1970

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,&apos; only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,&apos; and that the solid solution is quite limited in the MnO-MnS system.&apos; The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1&apos; and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

Brushy Creek mine is located near the center of a linear, 40 mile long belt of mineralization that extends south from St. Joe Minerals Corp.&apos;s Viburnum division. The mine area includes a segment of 5.4 miles long of this new mining region along which eight mines are presently operating. The geology of the area is relatively simple; the rock formations have not been disturbed through folding or extensive faulting.

Jan 7, 1973

By Frederick Laist

The ores received at the Washoe Smelter come almost entirely from the mines in Butte and contain the following minerals : Chalcocite, Cu2S; covellite, CuS; chalcopyrite, CuFeS2, (trace); bornite, Cu3FeS3; enargite, Cu3AsS4; malachite, Cu2CO4 + H2O (trace); pyrite, FeS2; sphalerite, ZnS; rhodo-chrosite, MnCO3, (less than 1 per cent.); rhodonite, MnSiO3, (less than I per cent.). The country-rock of Butte is of the granite family and is a quartz-monzonite containing a little less silica than typical granite. It is made up of the following rock-minerals in approximately the proportions indicated: Minerals. Composition. Per Cent. Quartz SiO2 20 Andesine 1/2 NaAlSi3O8; 4 CaAI2Si2O8 42 Orthoclase KA1Si308 23 Hornblende 1/2 Ca(MgFe)3Si4O12; & (MgFe)2(AlFe)4Si2O12 6 Biotite (HK)2(MgFe)2A12Si3O12 9 Titanite CaTiSiO5 0.1 Apatite (CaF)Ca4(PO4)3 0.05 Magnetite (FeO)(Fe2O3 0.15 Pyrite FeS2 0.02 99.32 The main country-rock (quartz-monzonite) is cut by dikes of aplite, a granite having the following composition: Quartz, 30; andesine, 20; orthoclase, 45; ferro-rnagnesian minerals, 3; pyrite, 0.1; total, 98.1 per cent. Closely associated with the copper-deposits are dikes and bodies of " Modoe" porphyry, technically known as quartz-

Jan 1, 1913

A new $18-million hydrometallurgical ore treatment facility for the recovery of molybdenum oxide was dedicated at Climax, Colo., on November 19 by Climax Molybdenum Co., division of AMAX. The Company has been producing molybdenum from molybdenite (MoS2) ores since 1918. Now oxide values, formerly lost in the sulfide flotation plant tailing are to be processed to yield about 3 million Ib per year of metal. In 1965, Climax produced about 50% of world molybdenum from sulfide ore. This ore is mined at the rate of 42,000 tpd. The annual production of concentrate is 100 million lb containing 90% to 92% MoS2, or about 50 million lb of metal. As only a relatively small portion of the total Climax production is sufficiently enriched in oxide molybdenum to process through the new plant, 5700 tpd of selected ore containing 1.5 lb of Mo per ton is now treated by the new process.

Jan 12, 1966

By T. Tanaka, H. Kiuchi

The combination of the following two exothermic reactions was studied with the purpose of recovering H2 from H2S formed in acid leaching of sulfide ores, direct reduction of metal sulfides with H2 or desulfurization of crude oils: In the kinetic study of the recovery of H2, the reaction rate was measured by the two methods of single-stage and circulation blowing of H2S through molten Pb in the temperature range of 550 to 750°C. The experimental results showed that the rate determining step is in the chemical reaction itself and also that this reaction is accelerated markedly by the addition of a trace of Ni, which may be responsible for the catalytic action of Ni dissolved in molten Pb. In the experiments where Pb metal was produced, PbS was oxidized in a stream of atmospheric N2 containing 0.5 to 20 vol-% 02 or in the same 02 partial pressures as in N2 though under reduced pressures in the temperature range of 400 to 800°C. It was found from these experiments that the formation of PbSO4, basic sulfates and PbO are suppressable to yield Pb metal alone above 750°C and for 02 concentrations of less than 1 vol-%. Vapor of PbS was thought to take an important part in the Pb formation mechanism, and the probability thereof was demonstrated thermodynamically.

Jan 1, 1978

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K&apos;l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 &apos; at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K&apos;1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken&apos;s10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- &apos;, and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By Parke A. Hodges

CHROMIUM, one of the most vital of the strategic metals, has constantly increasing importance as research expands potential uses in alloy steel metallurgy. All signs point to a steadily growing use for chrome ore, and the general subject has received a great deal of attention recently.1 A relatively little known country, Southern Rhodesia produced a total of 5.949 million tons, or 18.6 pct of the total world chrome output, between 1906 and 1950, according to figures from the U. S. Dept. of Commerce. According to U. S. Bureau of Mines figures, Southern Rhodesia produced 291,525 tons in 1950 and 300,267 tons in 1951, or approximately 13 and 11 pct, respectively, of world production for the two years. In 1953 the Rhodesian Vanadium Corp. produced about 85,000 tons of which probably 7,000 tons were concentrate. Production by other companies was high. Large in themselves, the figures assume even greater significance because most of this output is of metallurgical grade.

Jan 8, 1954

By Frank Van Horn

INTRODUCTION IN June, 1911, the writer spent a few days in studying the economic geology of the vicinity of Park City. During this rather hurried visit a number of specimens of ore were collected, which have since been examined. The results of these investigations show that bournonite (PbCuSbS3) is present in the ores in greater or less quantity. This fact has never before been reported, as far as can be learned. The failure to recognize this mineral is due to its similarity to tetrahedrite, with which it has probably been confused during a long period of years. Jamesonite (Pb2Sb2S5) has been reported from the region in a rather doubtful manner, but the writer has seen it in notable amounts from several mines, and can offer the first analysis of this mineral from the district. Calamine (H2Zn2SiO6) was found at one mine and has never been recognized and reported from the district.

Jan 8, 1914

(The following list contains the names of those members of the Institute of whose connection with military service we have only recently become acquainted; it also includes the names of a few who have recently been promoted or transferred, indicated by a *. A complete list was published in the Year Book, issued as a supplement of the Bulletin for March, 1918.) ANDERSON, AMIL A., Co. A, 309th Regiment Engineers, 84th Div., American E. F., Care Postmaster, New York. ARMSTRONG, HAROLD K., Pilot, Naval Aviation, U. S. Naval Air Station, Miami, Fla. BASSETT, ARTHUR F., Co. 6, -E. 0. T. S., Camp Humphreys, Va. BEDDALL, THOMAS H., Adjutant, 1st Battalion, 1st Gas Regiment, American E. F. BERNARD, CLINTON P., Candidate, 12th Observation Battery, F. A. C. 0. T. S., Camp Taylor, Ky. BROOKE, LIONEL, 50th Co., 13th Battalion, 5th Replacement Engineers, Camp Gordon, Ga. BROWNING, EDWARD, Corp., 1st Regiment Engineers, Co. D, American E. F. BUGBEE, EDWARD E., S. A. T. C. Headquarters, Raleigh N. C. BUTTERFIELD, G. BRUCE, CO. C, 605th Engineers, American E. F. CADOT, J. J., 1st Lieut., U. S. Air Service, American E. F., Care Post- master, New York. CARLOCK, J. B., Major, 2d Battalion, 1st Gas Regiment, American E. F., France.

Jan 12, 1918

By Paul R. Wieber, Atam P. Sikri

This paper describes the U. S. Energy Research and Development Administration&apos;s (ERDA) program to develop in situ coal conversion processes, especially gasification. The potential of this technology, the technical directions being explored, and the program strategy to carry the process concepts toward commercialization are emphasized. The geographic location of the U. S. coal resources and a market analysis are described. Commercially successful in situ coal processes could add over a trillion tons of coal to the U. S. coal reserves. The economics of these processes is compared with surface gasification. Independent studies show this process to be 25% cheaper than surface gasification for Western coals. The major projects are briefly described. The Linked Vertical Well process is in the most advanced stage and shows great promise. The last test produced a low-Btu gas averaging 171 Btu per standard cubic foot for average production rates of 8.5 million standard cubic feet per day. The other projects are Packed Bed, Longwall Generator, and Steeply Dipping Beds. Unique factors of the process development are discussed which may lead to commercial processes in the near term. A development strategy is proposed by which this technology could be commercialized before 1985 with potentially lower gas prices and lower environmental impacts, relative to mining plus surface gasification.

Jan 5, 1978

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By P. Shahinian, M. R. Achter

P. Shahinian and M. R. Achter (U.S. Naval Research Laboratory)—We should like to point out another instance where concentration of impurities in grain boundaries led to an embrittlement. In this case an impure nickel (99.8 pct) developed many more in-tergranular cracks during creep in a nitrogen atmosphere than in vacuum.5 In comparison high-purity nickel (99.99 pct) exhibited a much smaller atmosphere effect. We concluded that the interartion of the nitrogen with nitride-forming impurities concentrated at grain boundaries promoted inter-granular cracking.

Jan 1, 1965

By S. P. Ray, B. D. Sharma

THE activation energy values for self-diffusion in pure metals have been correlated with a number of physical properties such as melting points,1 valences,&apos; Debye temperatures,3 and cohesive energy densities.4 Extending the melting point correlation, the self-diffusion activation energy values for the alloys can be similarly correlated with the solidus temperatures. For metals and alloys which exhibit phase transformations, such a correlation is not feasible because of the uncertainty of various physical properties of the corresponding phases. Using thermodynamical approach, Ardell5 calculated the hypothetical melting points of the low melting phases of the polymorphic metals. However, these calculated melting points do not show reasonable correspondence with the activation energy of self-diffusion. Recently, a new approach treating metals and alloys as electron concentration phases has been developed by Engel6 and Brewer.7 These workers have attempted to correlate the crystal structures with the electron configurations of the atoms existing either in ground state or in an excited state of low promotion energy. The basic postulate of this theory is that whereas the contribution to the bonding of the metal comes from the interaction of both d and (s-p) electrons existing either independently or in hybridized states, the existing crystal structure is controlled by the (s-p) electrons alone. Specifically, a metal is supposed to crystallize in bcc, hcp, or fcc phase provided the metal has one, two, or three valence electrons per atom in the (s-p) configurations. The diamond, or ZnO and ZnS structures, occur with four (s-p) electrons per atom. Secondly, the contribution of d electrons to bonding is supposed to increase with atomic number

Jan 1, 1970

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.&apos; However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By Y. C. Liu, R. H. Richman

The effects of gel,manium and tin on the deformation and 9-e-crystallization textures of copper have been explored in detail with in the copper-rich terminal solid solutions. Addition of solute to copper produces a change in deformation texture from the copper type to the 70 :30 brass type. This transition has been measured quantitatively The types mid proportions of recrystal-lization components have been determined as a function of com-position, and correlation of recrystallization components with specific deformation components is discussed. On the basis of information available in the literature, it has been suggested that the effect of solute elements on the recrystallization texture of copper

Jan 1, 1961

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,&apos; and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.&apos; Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8&apos;7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8&apos;9 Copper minerals sometimes yield elemental sulfurlo&apos;" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,&apos;5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By M. E. Fine

IN the apparatus for measuring internal friction shown in fig. 1, a modification of that described by Kê,1,2 the parasitic energy loss or background is equivalent to a Q-1 of approximately 4x10-5. This low value of background was obtained by using a jeweler&apos;s collet of appropriate size for the upper support, eliminating lateral motion without immersing the bob in oil, and designing the bob to reduce air resistance. The pendulum is supported on the frame through a snug fitting, sliding rotary joint (fig. I-B). A slight twist of the top imparts essentially pure torsional motion to the pendulum. No evidence of energy loss in the sliding joint has been observed. In the bob (E) steel balls are used in the torsion arm, and the bottom is filled with lead giving a total weight of 94 g. A lighter bob may be used for small diameter specimens. Another bob was a solid disc with provision for adding discs to change the frequency. The oscillating image of the filament is recorded on a revolving drum camera (fig. 1-3) driven by a synchronous motor. This allows use of frequencies higher than can be measured visually on a glass scale. Samples varying in diameter from 0.020 to 0.075 in. have been measured, the frequencies have ranged from 1 to 12 cps, and the maximum strain varied from 0.5 to 10x10-5. With appropriate modification the sample may be placed in a thermostat. The apparatus may also be used to measure the shear modulus. In the examples of measurement given in table I the internal friction of Permendur and the 46.8 Ni-Fe alloy are due, for the most part, to magneto-mechanical hysteresis8 (elastic hysteresis accompanying stress-induced magnetostriction) which depends on strain amplitude and increases with annealing. The internal friction of most materials decreases with annealing. References IT. S. K6: Physics Review (1947) 71, 533. 2 T. S. Kê: Transactions AIME (1948) 176, 448; Metals Technology (June 1948) TP 23703. 3 R. Becker and W. Döring: Ferromagnetismus. 365 (1939). J. Springer.

Jan 1, 1951