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By Amitava Gangulee, Michael B. Bever

The order-disorder transition in Ag-Mg alloys in the range 17 to 26 at. pct Mg was investigated and some thermodynamic, electrical and mechanical properties of ordered Ag-Mg alloys were measured. A modification of the phase diagram is proposed on the basis of measured transition temperatures. The stability of the ordered structure is analyzed in terms of the quasichemical theory. Kinetic aspects of the order-disorder transition were also investigated. The energies of ordering at 273°K of Ag-Mg alloys were measured by liquid metal solution calorimetry. The electrical resistivities and the tensile Properties of the ordered alloys were measured. The exothermic energy of ordering increased with magnesium concentration up to the composition Ag3Mg; it is discussed in terms of the quasichemical theory. Pronounced order hardening was observed and can be explained by several strengthening mechanisms, which are particularly effective because of a change in crystal structure associated with the ordering transition. IN silver-rich solid solutions containing approximately 17 to 26 at. pct Mg, long- range ordering may occur during appropriate therma1 treatments. Clare-brough and Nicholas1 first detected such long-range order in the solid solution of composition Ag3Mg and suggested that the unit cell of the superlattice contained 256 atoms. x-ray2 and electron diffraction3 investigations confirmed the occurrence of long-range order, but indicated a shifted Ll2-type structure. On the basis of recent X-ray measurements the crystal structure of ordered Ag3Mg has been confirmed as type D023.4 The present paper is concerned with the order-disorder transition in silver-rich Ag-Mg solid solutions and some thermodynamic, electrical, and mechanical properties of the ordered alloys. The effects of short-range order on the properties of silver-rich solid solutions containing up to 26 at. pct Mg are discussed in a concurrent paper.5 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Specimens of Ag-Mg alloys containing from 18 to 26 at. pct Mg were prepared in the form of 1.0-mm-diam wires as described in Section 1.1 of Ref. 5. Disordered specimens were prepared by annealing at 773°K for 1 hr and quenching into iced brine. Ordered specimens were prepared by annealing at 773°K for 1 hr and slowly cooling to room temperature over a period of 15 days. The specimens were stored at 78°K. 1.2) Resistivity Measurements. Electrical resistivi- ties were measured by a potentiometric method.' Equilibrium values were obtained at several temperatures. The kinetics of ordering were investigated by following the time-dependent changes of the resistivity of initially disordered specimens during annealing. The specimens were enclosed in copper capsules and immersed in salt pots; the heating up was accelerated by injecting preheated helium into the capsules. 1.3) Calorimetry. The energies of ordering of the alloys were measured in a tin solution calorimeter as the difference between the heat effects of additions of completely ordered and disordered specimens of the same composition. The procedure and the method of calculation have been described.6 Magnesium was used for thermal compensation in most calorimetric runs in order to improve the accuracy.677 1.4) Mechanical Tests. Tensile tests were carried out with wire specimens at room temperature as described in Section 1.5 of Ref. 5. Microhardness measurements were also made.? 2) RESULTS AND DISCUSSION The characteristics of the order-disorder transition of silver-rich Ag-Mg solid solutions will be discussed first. Some thermodynamic, electrical, and mechanical properties of the ordered alloys will then be considered and compared with the corresponding properties of dis-disordered alloys. 2.1) The Order-Disorder Transition. 2.1.1) Thermodynamic and Structural Aspects. The transition temperatures Tt were determined from discontinuities in the slope of the equilibrium resistivity vs temperature curves. Normalized curves for three compositions are shown in Fig. 1. The transition temperature increases with the magnesium concentration and reaches a maximum at the stoichiometric composition Ag3Mg. The transition temperature of the alloy Ag3Mg was measured as 665° ± 2°K and compares with published values of 660°,1 663°,8 and 66°k.3 In the slopes of the resistivity vs temperature curves of alloys containing 22.2 and 22.5 at. pct Mg, discontinuities were observed at two temperatures. Such upper and lower discontinuities indicate a two-phase field. A modified form of the published phase diagram9 is shown in Fig. 2. A two-phase field was found only on the low-magnesium side of the composition Ag3Mg. On the high-magnesium side, the existence of a two-phase field could not be established because of insufficient resolution, but such a field must be present. This part of the phase diagram can be made complete by a eutec-toid-type reaction a = (a' + ß). The existence of a boundary between the two-phase fields (a + ß) and (a' + ß) is also in accord with published lattice parameters.3 The crystal structure of ordered Ag3Mg (type Do23)

Jan 1, 1969

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By Elmars Ence, Harold Margolin

The Ti-Fe and Ti-Fe-0 systems were re-examined because of the controversy regarding the existence of Ti2Fe, and to consider all available data points to the existence of Ti,Fe. The Ti-Fe-0 system contains two ternary compounds: E, corresponding to Ti2Fe; and y. SEVERAL authors have investigated the constitution of titanium-rich alloys of the Ti-Fe system. The most extensive study of titanium-rich portions of the Ti-Fe system was by Van Thyne, Kessler, and Hansen,' who investigated this system up to 50 pet Fe and used the highest purity materials available for their alloy preparation (iodide titanium was used for alloys up to 20 pet Fe). According to Van Thyne et al., phase relationships in the region of investigation are governed by phases a,ß, and TiFe. No evidence of an intermetallic compound Ti,Fe was found. although earlier. works by Laves and Wallbaum,' and Duwez and Taylor' reported its existence. Rostoker's study on the occurrence of TilX phases" confirmed the findings of Van Thyne et al. Rostoker proposed that the compound Ti Fe found by Duwez does not exist but is actually a ternary compound, Ti1Fe3O, originated by inadvertent oxygen contamination. The partial isothermal section of the ternary Ti-Fe-0 system as reported by Rostoker' seems to confirm this explanation. In the course of phase diagram work conducted at New York University, however, certain irregularities were observed to be associated with ternary systems of the type Ti-Fe-X. The ternary phase 6, observed in the systems Ti-Fe-Mo' and Ti-Fe-V." was found to be structurally identical to the com-pound Ti2Fe as reported by Duwez and Taylor, and to Rostoker's compound Ti1,Fe2O. Since the amount of oxygen possibly present in the Ti-Fe-Mo and Ti-Fe-V systems could not account for the observed amounts of the compound, it appears that the d phase in these systems is not Ti,Fe,O. On the other hand, considering the amounts of the 6 phase, particularly in the Ti-Fe-Mo system, the location of the phase was uncertain. It was felt that the introduction of the Ti2Fe phase would alleviate some of the inconsistencies of the two systems. Because of the uncertainties relating to the phase Ti2Fe, or Ti1Fe2O, it appeared worthwhile to re-examine the Ti-Fe and Ti-Fe-O systems in the vicinity of these compounds with highly sensitive metallographic techniques and with X-ray methods. Experimental Procedure Alloy Preparation—For the study of the binary system four alloys were prepared, containing 26.9 (30 wt pct), 34.0 (37.5 wt pet), 41.2 (45 wt pet), and 56.3 (60 wt pet) atomic pet Fe, and for the ternary Ti-Fe-O system 18 alloys were prepared in the composition range of 1.6 to 16.9 atomic pet 0 and 24.3 to 55.7 atomic pet Fe. The materials used for the Ti-Fe alloys were iodide titanium (99.98 pet Ti, 0.002 pet 0) and Ferro-vac-E iron (99.95 pet Fe, 0.0052 to 0.0072 pet 0). For the Ti-Fe-O study the materials used were sponge titanium containing less than 0.06 pet 0, Ferrovnc-E iron, and Baker's analyzed TiO2. The nominal weight and atomic percentages of the ternary alloys prepared are shown in Table I. Melting—Charges of 10 to 15 g were melted in a nonconsumable arc furnace in argon atmosphere according to the technique described elsewhere.'" Since there was practically no weight loss through the various stages of melting and oxygen losses have not been observed previously, it appeared justifiable to use nominal composition for interpretation of data. Iodide titanium control buttons, of the same mass as the Ti-Fe charges, and melted under the same conditions, were used to check hardness pickup during melting. A hardness increase of 2 to 3 Vhn was found. Heat Treatment—The specimens were annealed in quartz capsules under argon. To avoid contact between the specimen and capsule material all specimens were wrapped in titanium sheet. The annealing times are given in Table 11. The attain-

Jan 1, 1957

Oct. 8-13, 1917 The St. Louis Meeting of the Institute will be held Oct. 8-13, 1.917. Various committees are being organized to perfect the arrangements for the meeting. A number of excellent technical papers have already been secured end an attractive series of excursions has been outlined. The following is the outline plan for the meeting. More detailed announcements will be made as the plans mature. MONDAY, OCT. 8 Morning: Registration and Technical Session. Afternoon: Boat ride to Herculaneum, Mo., to visit smelter. and Evening: Dinner on boat and social evening.

Jan 4, 1917

NEW MEMBERS The following list comprises the names of those persons who became members during the period Feb. 10, 1919, to Mar. 10, 1919. ALLEN, ROLLAND CRATEN State Geol., Appraiser of Mines, Lansing, Mich. ALTMAYER, MAURICE ERNEST, Ingenieur des Arts et Manufactures, 145 Rue de la Pompe, Paris, France. AUSTIN, CHARLES L., Assayer, Highland Boy Mine, Utah Cons. Min. Co., Bingham Canyon, Utah. BARTLETT, ARTHUR J., Chief Engr., Louisville Coal & Coke Co. Goodwill, W. Va. BOIES, ORLOW W., Research Chem., Roessler & Hasslacher Chemical Co., 1632 Tenth St., Niagara Falls, N. Y. BRAGG, G. A., Mgr., Experimental Copper Leaching Plant, Mellon Inst. of Industrial Research, Thompson, Nev. BRUSCANTINI, GIOVANNI, Min. Engr., Gen'l Mgr., Sindicato Minero de Cuba, Box 370, Santiago, Cuba. COLONY, R. J Instructor in Geol., Columbia University, New York, N. Y. DAVENPORT, FRANK B., Cons. Engr., 806 Coal Exchange Bldg., WiIkes-Barre, Pa. EATON, S. FORD 120 E. 85th St., New York, N. Y. EBY, J. H., Min. Engr Box 433, Spokane, Wash. ENGELHARDT, EDWARD A., Mgr., Surinaamsche Bauxite Mij, Paramaribo, Dutch Guiana, S. A.

Jan 4, 1919

By C. C. Hawes

SILICA is the main impurity in iron ore. It is intimately associated with the iron oxide, sometimes free but more often in the combined state, as a mineral silicate. Its separation and purification sometimes present difficult problems to the analyst. In the absence of any definite knowledge to the contrary, orthosilicic acid. H4SiO4, is supposed to be the only silicic acid made, all other forms, such as metasilicic acid, H2SiO3, representing different degrees of its dehydration. These acids are exceedingly weak but form the most stable compounds found in nature. They are known as the silicate minerals and are formed by the combination of the different metallic oxides

Jan 1, 1936

By John E. Murphy, Ernest L. Ohle

Hematite-magnetite ore bodies at Iron Mountain, Missouri, have produced nearly 9 million tons of iron ore concentrates since 1844. The ore minerals occur principally as open-space filling in fractured and brecciated andesite porphyry with very minor replacement of the wall rocks. The enclosing rocks are Precambrian in age and consist of a series of dacite, rhyolite, and andesite flows aggregating about 2000 feet in thickness. All of the ore is in andesite and the mineralization is Precambrian in age. The shape of the ore bodies, the breccia character of the ore, and the gangue mineralogy are believed to be unique. One of the two main ore bodies is crudely dome-shaped with a tendency for development of concentric mineralized shells; the other is an elongated lense in plan but hook-shaped in cross section. Both have strong linear elements striking northeast, east-west, or northwest. Various modes of origin for the structures and for the tension breccias have been suggested, but none is completely satisfactory. Hematite is the main ore mineral; magnetite is subordinate. Important gangue minerals are andradite, quartz, calcite, actinolite, apatite, epidote, and chlorite. Although some evidence favors injection of an iron-rich melt, other evidence suggests ore formation by a high temperature, water-rich solution.

Jan 1, 1968

By W. H. Caruthers

ECONOMIC utilization of all by-products has long been the goal of American industry. One of the first groups that was popularly supposed to have achieved its aim was the meat-packing industry, which reputedly found a use for everything except the squeal of the hog. To the metallurgist, slag has always been the principal wasted by-product, representing a loss not only of material, but of heat. Slag does not possess many qualities that appeal to man's imagination or suggest a romantic influence on the daily life and progress of a community or nation. It is a bulky product, and space for its disposal within reasonable hauling distance of a smelter is not always available; the iron-ore smelter especially has been wont to find space for slag disposal at a premium. Therefore, the success that has been attained in recent years in finding a use for iron blast-furnace slag is notable. It has become a vital economic factor in the construction industry in areas where it is available. Its use may suggest further possibilities of an economic outlet for the slags from nonferrous smelting as well.

Jan 1, 1940

The following is an incomplete list of members and guests who called at Institute headquarters during the period Jan. 10, 1918 to Feb. 10, 1918: K. Baumgarten, San Diego, Cal. J. A. Meyerovitch, Petrograd, Russia. F. J. Brine, Toronto, Ont., Canada. C. Naramore, Washington, D. C. W. A. Castleton, Salt Lake City, Utah. Orrin P. Peterson, Wausau, Wis. J. Ross Corbin, Boyerton, Pa. William H. Rea, Pittsburgh, Pa. W. M. Corse, Buffalo, N. Y. W. Murray Sanders, Tucson, Ariz. W. A. Deane, Summitville, N. Y. Edmund F. Saxton, Philadelphia, Pa. S. E. Doak, Philadelphia, Pa. William C. Schmidt, Humboldt, Ariz. F. G. Downs, Jersey City, N. J. G. J. Sielaff, Oakland, Cal. Albert H. Fay, Washington, D. C. A. D. Sproat, Bound Brook, N. J. F. Julius Fohs, Tulsa, Okla. J. A. Stader, Joplin, Mo. A. L. Gholz, Minneapolis, Minn. A. K. Stewart, Mine La Motte, Mo. Ruger W. Hay, Easton, Pa. Geo. W. Tower, Jr., New Rochelle, N. Y. Stanley C. Herold, Pittsburgh, Pa. Henry Traphagen, Toledo, Ohio. A. A. Holland, Montreal, Canada. H. E. Treichler, Chuquicamata, Chile. T. Z. Humphrey, Anaconda, Mont. Paul M. Tyler, Fairlee, Vt. H. M. LaFollette, LaFollette, Tenn. F. R. Van Campen; Seattle, Wash. J. B. Lain, Goldfield, Nev. Thor Warner, Phoenix, Ariz. J. R. Lashbrooke, Los Angeles, Cal. Clarence Woods, Narrows, Va. W. F. Lewis, Ewen, Mich. E. N. Zern, Pittsburgh, Pa. C. E. McQuigg, New Haven, Conn. Robert J. Anderson has resigned his position as chief chemist and metallurgist of the Cleveland Metal Products Co., Cleveland, Ohio.

Jan 3, 1918

ALABAMA. Aldrich, Aldrich, W. F. Anniston, Noble, A. E. Auburn, Brown, R. L. Bessemer, Abbott, C. E., Ferguson, V. Birmingham, Aldrich, T. H., Aldrich, T. H., Jr., Allen, A. W., Bowron, J., Burbidge, T. A., Crawford, G. G., Crockard, F. H., Davis, F. H, Dimmick, F: D., Ellis, E. E., Geismer, H. S., Hiller, E., Johnson, G. R, Ludwig, C. P., McCormack, G. B., McCrery, Peters, R, Jr., Phillips, W. B., Pill, J. R., RamSay, E. Coal City, Pattberg, 0. F. E-msley, Wil¬liams, E. P. Helena, Squire, J. Holt, Shook, J. W. Huntsmlle, Moss. Ironton, Hudson, J., B. Lehigh, Toulmin. Bock Bun, Garvin, J. M. Woodward, Wood¬ward, A. H.

Jan 1, 1910

By H. Stuart, L. Zwell, N. Ridley

specimen that was subjected to 700°C for 250 hr is shown in Fig. 2(c). The precipitates in this foil appear round and exhibit only very faint strain contrast. From this evidence, along with that described above for the symmetry of the strain field, it may be concluded that this coherent precipitate is spherical, which is generally the favored shape for coherent precipitates when the lattice parameter mismatch is small.12 These observations are consistent with the assumption that this precipitate is the y' (Ni3Al, Ti) phase. y' is known to be spherical in the early stages of precipitation. It is fcc and is similar in composition to the matrix and thus would have contrast similar to that of the matrix as do these precipitates. Direct identification of the spherical precipitate did not prove possible because of its low volume fraction and small size. The results of this investigation suggest that the increases in yield strength and the decreases in elongation observed in 45-Fe 30-Ni 20-Cr alloys containing about 0.4 pct A1 and 0.4 pct Ti on prolonged aging at 550" to 700°C are very likely due to the presence of a coherent, spherical precipitate, thought to be y'. Mi-crohardness measurements indicated that the precipitation of semicoherent M23C6 resulted in some matrix hardening. However, this precipitation process occurs much more rapidly than the changes in mechanical properties at these temperatures. 1C. L. Clark, J. J. B. Rutherford, A. B. Wilder, and M. A. Cordovi: J. Eng. Power, 1962, vol. 84, p. 258. 2 F. A. Comprelli and U. E. Wolff: USAEC Report GEAP-4745, General Electric Company November, 1964. 3C. N. Spalaris: A Monograph, USAEC Report GEAP-4633, General Electric Company, July, 1964. THERE have been many X-ray investigations of the room temperature lattice parameters of austenite which has been retained in quenched steels of various carbon contents. The results of these investigations have been collected by Wrazej,1 Wever et al.,2 and by Roberts3 and are included in Fig. 1 due to Pearson.4 The dashed line in Fig. 1 was considered by Roberts3 to most reliably describe the variation with carbon content of the lattice parameter of retained austenite. This line is given by the equation: a (Å) = 3.555 + 0.044 wt % C and recent unpublished measurements by one of the authors (LZ) support this relationship. The object of this communication is to draw attention to a relationship which describes the variation of the room temperature lattice parameter of 'equilibrium' austenite with carbon content, and which is different from that for retained austenite. The relationship a(Å) = 3.573 + 0.033 wt % C has been obtained from lattice parameter measurements made on equilibrium Fe-C austenites at elevated temperatures, which have been extrapolated to room temperature. The room temperature lattice parameter of 3.555Å which the Roberts' relationship gives for pure y-Fe is no: in agreement with the value of 3.573Å obtained when the high temperature lattice parameter data of Basinski et aL.5 and of Goldschmidt6 is extrapolated to room temperature. A linear extrapolation was

Jan 1, 1970

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961

By H. D. Keiser

Minor industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz, and nonfuel gases (air, helium, carbon dioxide). Alum Minerals The natural alums comprise a group of hydrated double sulfates, the most important of which are potash alum, KAI(S04)2.12H20, the "alum" of popular usage; ammonium alum, (NH4)AI(SO4)2, known mineralogically as tschermigite; and soda alum, NaAI(SO4)2.12H20. Kalinite, KAI(SO4)2.11H20, and mendozite, NaAl(SO4)2, 11H20, are fibrous monoclinic alums, distinct from the isometric species potash alum and soda alum.4 Alunite, KAI3(S04)2(OH)6, also known as alumstone or alum rock, has been used as a raw material in the manufacture of alum since early times. All the natural alums are highly soluble and occur as surface evaporation products in arid regions or in sheltered places. Potash alum, together with the other natural alums, commonly occurs as an efflorescence or crevice filling in argillaceous rocks and brown coals that contain disseminated pyrite or marcasite. The mineral is derived by the action of sulfuric acid, formed during the weathering of the sulfide, upon alkali-rich aluminum silicates. Ammonia alum is found chiefly in lignite or broad-coal beds and bituminous shales. Alunite is most commonly associated with acid volcanic rocks, where the rock has been largely altered and alunite formed owing to the presence of sulfuric acid solutions or vapors. Aluminum sulfate, which for most uses is the essential ingredient of alum, may be found in saline residues resulting from the evaporation of natural water and may be formed by the action of acid waters upon aluminous rocks. A deposit of natural potash alum occurs in an irregular network of veins associated with sulfur in rhyolite in Esmeralda County, Nevada, about 35 miles west of Tonopah and 10 miles north of Silver Peak. Alum was recovered at a plant operated on the property between 1920 and 1923 by crushing the ore to ¾ in., grinding to minus 80-mesh, and counter-current leaching; the resulting alum solution was then filtered and crystallized. Alunite was of much interest during World War I as a source of potash and during World War II as a source of alumina. The wellknown deposits at Tolfa, Italy, are veins in trachyte and have been the basis of alum manufacture there since the middle of the fifteenth century. Pure alunite is insoluble in water and in common acids, but if it is heated to 500°C it loses its water of hydration, and the residue consists largely of anhydrous potash alum, part of which is readily soluble in water or acids. If the heat is increased beyond 500°C, most of the sulfur combined with the alumina is released as oxides and the residue consists of potassium sulfate and alumina. Thus, either potash alum (and aluminum sulfate) or potassium sulfate and alumina may be made. In the

Jan 1, 1960

By L. T. Leyson, U. C. Tainton

Some time ago, at ameeting of the Institute Prof. J. W. Richards1 said, "I take exception to the statement that all the factors in the production of electrolytic zinc were known long ago.... There is possible in my opinion an improvement of perhaps 50 per cent. in the new electrolytic processes." An examination of the literature of the subject will show the justness of Professor Richards' contention. The work of the earlier investigators was carried on in the shadow of difficulties that, today, are hardly more than memories. We seldom hear now of zinc sponge, that bête noir of the electrolytic-zinc pioneers. Zinc sponge was the name given to a peculiar, soft, black, non-adherent form of zinc deposit that was utterly useless for melting into ingot form. At the big plant at Cockle Creek, New South Wales, in 1897, Edgar Ashcroft2 said that the solution in the plant would suddenly, and without ascertainable cause, go' "bad" and begin to deposit spongy zinc. The most delicate, even spectroscopic, methods of analysis were unable to detect any difference between "good" solution and "bad" solution; either form might change to the other on being kept for a while. When it is added that an outbreak of this insidious disease (which appeared to be infectious, or at least contagious) could be dealt with only by discarding the solution and washing out all tanks and pipe lines, some idea may be gathered of the troubles of the zinc electrometallurgist in what may be spoken of as the "sponge age" of electrolytic zinc. Thanks to the efforts of a number of investigators, we are today able to diagnose with considerable certitude the nature of the malady that puzzled Ashcroft and his co-workers. The researches of Mylius and

Jan 1, 1924

By M. Albertson

UNITED STATES petroleum pro-dU6tion during 1937 materially exceeded? that of any previous year. Firm control of the production rate was maintained under State and Federal laws and aided by the' Interstate Compact. During the first ten months," crude oil prices were stable, except for a slight increase early in the year. Toward the end of the year, uncertainty of price structure be-came evident and a sharp reduction in allowable production was under way. Exploration for new pools and development of .pools already discovered continued active throughout the year. Production control agencies in Texas, and to a less extent in New Mexico and Louisiana, appear to have had increasing difficulty in holding crude oil output to allowable limits. The situation elsewhere is less well known but probably the same condition exists in other important producing States whether control is by State commissions or by unofficial bodies.

Jan 1, 1938

THE SOUTHWEST MINING SECTION of the National Safety. Council held a well attended two-day conference at Globe, Ariz., March 19 and 20; followed by two days of mine-rescue maneuvers at the Old Dominion mine in cooperation with the Globe-Miami District Mine Rescue and First Aid Association and the U. S. Bureau of Mines. C. L. Colburn of the Bureau had general charge of the arrangements and was chairman of the conference. All sessions were held in the Old Dominion Library. The program of papers was as follows: MINE FIRE PREVENTION AND FIGHTING What to do in Case of a Mine Fire. / Chas. A. Mitke, Consulting Mining Engineer, Bisbee, Ariz. Gunnite as a Fire Preventative. W. C. Browning, General Manager, Magma Copper Co., Superior, Ariz. Chemical Engineer's Part in Fire Fighting. Dr. L. H. Duschak, Consulting Chemical Engineer, San Francisco, Cal. Mine Fire Drills. A. C. Stoddard, Chief Mining Engineer, Inspiration Consolidated Copper Co., Inspiration, Ariz. Notes on the Installation of Fire Fighting Equipment in Mines. Benjamin F. Tillson, Assistant Superintendent, New Jersey Zinc Co., Franklin, N. J.

Jan 5, 1923

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

Bailey, Lewis Newton, Master Engineer, Senior Grade, 4th Regiment, U. S. Engineers, Headquarters Company, died of pneumonia at Camp Merritt, N. J., on April 30, 1918. Baird, Louis, Lieut., Royal Field Artillery, British Army, died on the battlefield in 1915. Ballamy, John H., Capt., 103c1 Engineers, killed in action near Fismes, Aug. 9, 1918. Bowles, Martin F., 2d Lieut., Co. B, 355th Infantry, killed in action, Sept. 3, 1918. Burt, Andrew, died in active service, 1916. Cobeldick, William Morley, Royal Engineers, died from gas poisoning on Oct. 7, 1915. Dougall, Ralph,. 4th University Co., Princess Patricia Regiment, killed in action early in the war. Evans, Alfred Winter, Lieut.-Col., New Zealand Rifle Brigade, D. S. 0., D. C. M., killed in action on Oct. 12, 1917. Gordy, Sheppard B., died in service, Oct. 9, 1918. Gorman, Thomas C., Lieut., Canadian Engineers, killed in France, Mar. 18, 1918. Hague, William, 1st Lieut., Engineer Officers' Reserve Corps, died in active service, Jan. 1, 1918.

Jan 1, 1919

By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938