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By C. B. Daellenbach, T. D. Tiemann

The prevention of quartz flotation by chelation of activating ions with the tetrasodium salt of EDTA in oleic acid flotation was investigated using a small vacuum flotation cell. It was found that flotation of quartz could be entirely suppressed in the presence of activating ions during complete flotation of hematite. It was further shown that the concentration of activating ions liberated from Wisconsin Gogebic taconite is sufficient to float quartz in an oleic acid system. Large tonnages of low grade siliceous iron ores occur on the iron ranges of the Lake Superior district. Although the lower grade nonmagnetic types are currently not of economic importance, they constitute a large future potential source of iron and steel, and hence have been the subject for extensive research on their beneficiation. TACONITES Of particular interest to the Dept. of Minerals and Metals Engineering at the University of Wisconsin have been the low grade nonmagnetic taconites of the Wisconsin Gogebic Range. These occur as five members of the iron formation and have been described in detail elsewhere.' Essentially they consist of an intimate mixture of hematite, goethite and quartz, with minor amounts of siderite, magnetite, iron containing silicates, and manganese minerals. A typical mean analysis based on the Bureau of Mines analyses' is: SiO2-52.50%, Fe2O3-43.40%, (Fe-30.38%), A12O3-1.15%, P2O5-0.07%, Mn2O3-0.29%, CaO-0.07%, (S-0.03%), Loss on ignition-2.00%. The quartz in these ores is of a microcrystalline variety,2 and so intimately associated with the iron oxide minerals that extremely fine grinding, in the order of minus 325 mesh, is required for liberation. During grinding and subsequent flotation, the concentration of quartz activating ions in the pulp becomes sufficiently high to activate quartz which floats along with the iron minerals in the presence of oleic acid. cook3 and co-workers concluded that oxidized iron ores released appreciable quantities of quartz-activating ions in water pulps. This is shown to be true in the present investigation. As a matter of fact, application of this phenomenon, as well as the intentional addition of activating calcium ions, is made use of in the an ionic flotation of silica from the iron oxide minerals.4,5 In view of the above, it becomes almost impossible to effect a sharp separation of quartz in the oleic acid flotation of the iron oxide minerals from these taconites, even with satisfactory liberation. This fact led to the current investigation to find a means of linking the activating ions with a chelating agent. The aim was to establish basic data for the quartz-water-oleic acid system which might not only be applicable to iron ores, but also to the flotation of other siliceous ores as well. EXPERIMENTAL METHODS Vacuum Flotation Cell: The vacuum flotation used in this investigation is similar to that used by previous investigators.6,7,8 The cell consisted of a 100 ml graduated cylinder with the lip removed. Vacuum from a water aspirator was applied to the cell through a trap; suitable tubing, and a rubber stopper inserted in the top of the cell. Constant absolute pressure was maintained by means of a manometer connected to the trap with a tee. Flotation: The required amount of activating ion solution was pipetted into a beaker. This was then diluted to 99.0 ml with water having a pH below that desired for the test, or so adjusted with HC1. After addition of 1.0 ml of oleic acid solution (2.0 mg oleic acid per ml), the pH was readjusted to the desired value with NaOH, and the entire solution transferred to the cell containing 1.5 gm of quartz. After vigorously agitating the cell and its contents for 2 min, the vacuum was applied to the cell and the estimated degree of flotation observed for a 3-min period. Activating ions studied included Ca++, Mg++, Al+++, and Fe+ + + added as chloride solutions. In addition,

Jan 1, 1964

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

[University of Alaska College, Alaska Mining Society MAURICE BUTLER, President EARL FOSSE, Secretary RAYMOND J. BARBER, Faculty Sponsor R. H. OGBURN, Counselor University of California Berkeley, California Mining Association THEODORE OLSEN, President ARTHUR K BOURRET, Secretary FRANK H. PROBERT, Faculty Sponsor GRANVILLE S. BORDEN, Counselor D. C. JACKLING, Associate Counselor Carnegie Institute of Technology Pittsburgh, Pennsylvania The Metals Society EDWARD J. BOYLE, President W. T. LANKFORD, JR., Secretary M. GENSAMER, Faculty Sponsor EDGAR C. BAIN, Counselor]

Jan 1, 1940

By J. J. Beeson

The second part of the paper includes a detailed account of the processes of secondary-enrichment which have been effective in producing the disseminated ores. While both parts present new features, it is hoped that the discussion on secondary chalcopyrite and bornite may be of interest to those who are engaged in the study of secondary processes in other districts. The excellent work' Economic Geology of the Bingham Mining District, by J. M. Boutwell, was published in 1905. Since that time the extensive development work-surface cuts and underground drifting-of the Utah Copper Co. has made possible the collecting of samples for more detailed microscopic study. The writer has taken advantage of this fact and presents the following work, not as a criticism, but as a' continuation of the work which was begun by Mr. Boutwell. b. Acknowledgments.-The present study was undertaken at the suggestion of Dr. A. F. Rogers; to him, and to Prof. C. F. Tolman and Prof. S. W. Young, the writer wishes to express his thanks for criticism in the preparation of this paper. The writer also expresses his thanks to D. C. Jackling, Vice-President and Managing Director of the Utah Copper Co., for permission to publish this paper, and to William Spencer, D. W. Wadleigh, T. S. Carnahan, J. A. Caulfield, Percy Dayer, and Edward Norsefall, for the courtesies extended to him while a co-worker in the mines.

Jan 11, 1915

By R. S. Shoemaker

Mines are closed for two reasons; exhaustion of ore or insufficient price for the mineral. On the other hand, the reopening of an old mine can be the result of any one of three events; the discovery of more ore, a sudden rise in the price of the product or the use of a new low-cost method of mining or milling the ore. Examples of the latter would be the open-pitting of an orebody previously mined underground as recently happened at Tyrone, N.M., or the adoption of acid leaching of an old pit as has been done at Miami, Ariz. The unique native copper mines of the Keweenaw Peninsula of upper Michigan have not been so fortunate. These deposits, which were first worked by prehistoric Indians, have been mined continuously from the early 1840's to 1968 when the last mines of Calumet and Hecla were closed and the Ahmeek mill. still using eight Nordberg steam stamps, was shut down. There are two types of deposits from which native copper is obtained; amygdaloid, which is a lava flow, and conglomerate, a sedimentary deposit of sand, rock fragments and pebbles cemented together. "In the amygdaloid, the copper is disseminated, or distributed much like the raisins in a cake; but in the rich Calumet conglomerate, the copper is more like a malleable rope or thread cementing the pebbles together." (C. Harry Benedict. Red Metal: The Calumet and Hecla Story, (Ann Arbor, Michigan, 1952), p. 42.) These deposits produced almost all of the copper used by the North in the Civil War and were substantial contributors to the copper needs of the United States in both World Wars. Some were mined to depths of as much as 9500 ft along the dip of the vein structure and 7500 ft vertically. Few of the mines ever really became worked out, but became uneconomical because of depth, pinching of veins or grades which dropped to about 1%.

Jan 5, 1972

[University of Alabama University, Alabama Mining and Metallurgical Society Meets first and third Mondays each month WILLIAM L. ALLMAN, President L. M. LOTOTZIY, Secretary J. R. CUDWORTH, Faculty Sponsor RICHARD L. BOWRON, Counselor University of Arizona Tucson, Arizona Miners' Society HARRY GARRETT, President AL WALLACH, Secretary A. J. THOMPSON, Faculty Sponsor E. D. GARDNER, Counselor Birmingham-Southern College Birmingham, Alabama Geology Journal Club WALTER WOLF, President LELAND CULLIGAN, Secretary R. S. POOR, Faculty Sponsor A. J. BLAIR, Counselor]

Jan 1, 1940

By E. F. Bailey, W. J. Harris

THE temperature of the ferrite to austenite re-action is established frequently by continuous heating experiments. However, equilibrium studies of this reaction have demonstrated that austenite may form at temperatures considerably below those at which the reaction is first observed during continuous heating. Because of this discrepancy, tempering is sometimes performed above the true critical temperature and in these cases austenite forms during tempering. The lowest temperature at which austenite forms and the kinetics of the reaction have been studied by Bain,' Bleakney and Gros-venor,2 and Dube and Cunningham. This austenite can affect the properties either as austenite per se, if it is retained at room temperature, or as a decomposition product if it transforms. The effect of austenite formation during tempering on low temperature impact properties of an 8 1/2 pct nickel steel was reported by Brophy and Miller4 in work published after the present investigation was initiated. They concluded that the improvement in low-temperature notch toughness which followed tempering at certain temperatures could be attributed to the austenite formed during tempering. Kramer et al.5 found anomalous hardness increases and embrittlement after tempering of a low-carbon manganese-nickel steel. They concluded that austenite formed during tempering, and that the decomposition products were responsible for the increase in hardness and the embrittlement. Quan-titative correlations of the microconstituents and mechanical properties were not made by these investigators. The present study was undertaken in order to establish the kinetics of formation of austenite at various temperatures, the characteristics of the decomposition of this austenite, and the relationship between mechanical properties and the phases present. Experimental Procedure A low-carbon manganese-nickel steel was selected because of the sluggishness of its austenite decom-position reactions. The composition of this steel in percent was: C, 0.10; Mn, 3.52; Ni, 2.34; Mo, 0.52; Cr, 0.17; Si, 0.19; V, 0.15; P, 0.019; and S, 0.020. Samples were prepared by forging sections from a large ingot to 3/4 in. bars. Formation and decomposition of austenite were investigated by dilatometric techniques which were checked by X-ray measurements. Dilatometer specimens were hollow cylinders 1 in. long, 1/2 in. diam, with a 1/8 in. central hole. All specimens were aus-tenitized for 1 hr at 1650°F and quenched in water prior to insertion in the dilatometer. Oxidation was prevented by using an inert atmosphere of purified nitrogen. Dilation was measured with a dial gauge which could be read by interpolation to 0.00005 in. Temperature was maintained within ± 3°F by a Brown Electronik Controller. Chromel-alumel thermocouple leads were welded to opposite ends of the specimen with the specimen serving as the hot junction. As a check on temperature uniformity comparison was made of the specimen temperature as measured with the chromel-alumel leads and the temperature of the center of the specimen as measured with a calibrated platinum—platinum-rhodium thermocouple embedded in asbestos in the central hole of the specimen. During heating a 5°F temperature difference was noted below 1000°F, but none above, while in cooling, a 5°F difference was observed from 1300" to 735°F, but none below. Heating rates of 35°F per min and cooling rates of 60°F per min were employed for all dilatometric studies. For transformation studies below room temperature, the dilatometer was allowed to cool to 150°F and then was quenched into liquid nitrogen.

Jan 1, 1951

By H. C. Fiedler

X HE development of the cube-on edge secondary re-crystallization texture in Si-Fe strip requires that normal grain growth be restrained. It has been shown that the degree of restraint and hence the completeness of secondary recrystallization depends upon the size and number of second-phase particles, which in turn is dependent upon the prior processing history.1y2 The purpose of this note is to show that, for heats in which manganese sulfide particles are providing the restraint to grain growth, the choice of hot rolling temperature depends upon the manganese content. The making and processing of the heats to the final gage of 0.012 in. has been described.3 The compositions are given in Table I. Apparent in Fig. 1 is the decrease in the ability of strips hot-rolled from 1175°C to undergo secondary recrystallization as the manganese content increases. It has been shown that 1175°C is below the solubility temperature of 0.014 pet S in even the 0.038 pct Mn alloy: and the observed behavior is attributed to an increasing fraction of the sulfur forming large manganese sulfide particles at the heating temperature for hot rolling. This fraction of the sulfur is thus unavailable to subsequently form the small, uniformly dispersed particles which are needed to restrain normal grain growth. Since the sulfur is completely in solution at 1325°C,3 strips from all three alloys show strong secondary recrystallization behavior when hot-rolled from that temperature.

Jan 1, 1969

By K. M. Rolls, J. Wulff, D. A. Colling

Solid-solution alloys of the Ta- Ti system containing up to 70 at. pct Ti were melted and fabricated into wire. Steady magnetic-field measurements of cold-worked wires at 4.2°K indicate that the resistive critical field increases smoothly with increasing titanium, reaching a maximum of 93 kG (J = 1 amp per sq cm) for a composition of about 50 at. pct Ti. The composition dependence of the resistive critical field indicates it is largely paramagnetically limited for alloys containing more than 35 at. pct Ti. For cold-worked wires the value of the critical current density, Jc , was found to be insensitive to composition changes for compositions in excess of 20 at. pct Ti. It was observed that Jc could be increased by final-size heat treatment at 400°C without altering the value of- the resistive critical field. Experimental data are used to calculate the electronic specific-heat coefficient and the "upper critical field" for the alloys studied. THE effect and importance of metallurgical structure on superconducting properties have been summarized by Livingston and Schadler.1 Specific work on solid-solution alloys such as Nb-zr2-7 and Nb-Ti5-7 have shown that critical current density (Jc) and superconducting transition temperature are structure-sensitive. Berlincourt et al.6,8,9 in their studies of transition-metal alloys find that Ta-Ti alloys remain superconducting at fields comparable to Nb-Ti alloys. 6,8 Transverse critical current tests of a Ta-10 at. pct Ti alloy10 and longitudinal critical current tests of a Ta-25 at. pct Ti alloy1' indicate that such alloys are capable of carrying high currents at intermediate fields (-40 kG). The work reported in the present paper was undertaken to explore the superconducting properties of further compositions in the Ta-Ti alloy system as well as the structure sensitivity of the superconducting properties. I) EXPERIMENTAL PROCEDURE Alloys were prepared by melting tantalum (Fansteel Metallurgical Corp., 99.96 pct purity) and iodide, crystal bar titanium (Foote Mineral Co., 99.92 pct purity) mixtures in an arc furnace on a water-cooled copper hearth using a tungsten electrode. Melting was accomplished in a purified, gettered argon atmosphere at pressures from 250 to 400 Torr. Each alloy was turned and remelted fourteen times to assure complete mixing of tantalum and titanium. Ex- cessive coring in the cast samples was, nevertheless, observed. This was somewhat reduced by annealing in vacuo at 1000°C for 13 hr. The ingots were then machined to 0.250 in. diam, jacketed in Type 304 stainless-steel tubing, and swaged to 0.140 in. diam. They were then drawn to 0.010-in.-diam wire. Alloys containing up to 70 at. pct Ti were readily cold-drawn to wire in this manner. Later experiments showed that oxygen additions up to -3000 ppm could also be cold-worked into wire. Test samples for superconductivity measurements in the 2-in, air-core Bitter solenoids of the M.I.T. National Magnet Laboratory were prepared from 10-in. lengths of 0.010-in.-diam wire, cleaned of residual wire-drawing lubricant. Current contacts were made by clamping clean copper tubing over both No. 18 current lead wire and the ultrasonically indium-tinned ends of the specimen wire.12 Potential leads of No. 32 copper wire were connected to the specimen by ultrasonic soldering in an indium bath. The potential lead separation was about 4 cm, corresponding to the circumference of the Bakelite rod to which the wire was affixed with half-mil Teflon tape. The final specimen configuration is shown in Fig. 1. Specimens were lowered into a liquid helium bath (4.2oK) in a double solenoid dewar and positioned so that the maximum magnetic field was oriented transverse to the wire axis of the gage section. Measurements were made by passing a current through the specimen at a preset solenoidal magnetic field. The current was increased until a 1-pv potential difference appeared across the gage section (1/4 µv per cm). At low magnetic fields, however, it was not possible to use this criterion because power-dissipation difficul-

Jan 1, 1967

By Albert Hahn

ABOUT three years ago John Hays Hammond took over the control of the Eureka Metallurgical Co., at Salt Lake City, Utah. Funds were advanced for investigating the process invented by R. V. Smith, for concentrating oxidized lead ores. A great deal of laboratory work was done and a reagent was developed by C. M. Nokes of Salt Lake, which was found to be particularly suitable for oxidized copper ores, refractory manganese silver ores, and oxidized gold ores. After sufficient laboratory work had been performed to demonstrate the fundamental principles of these inventions, a test mill, having a capacity, of 20 tons of ore daily, was erected at Murray, Utah. In this test mill approximately 1200 tons of various types of ores have been concentrated by means of the above-mentioned process and reagents, and this large-scale work as well as laboratory work is being continued at present. Details of these mill tests are given in Table 1, and a representative group of laboratory tests are shown in Table 2. The process requires no special machinery or appara-tus. Its success depends entirely, on the method of preparing the pulp and its subsequent flotation in clean water, as outlined in the Smith patent. The reasons for the success of the Nokes special reagent are not definitely known. The outstanding feature, which seems to be of extreme importance, is that when the concentrates are examined under the microscope, each particle of mineral appears to have a particle of paraffin, attached to it. This paraffin-mineral combination seems to be particularly suitable for flotation and it follows that any coating oils readily attach themselves to the paraffin-mineral combination.

Jan 9, 1923

By E. H. Rennhack

Phase equilibria of the zinc-rich portion of the Zn-Fe-A1 system containing up to 20.0 wt pct Fe and Al have been investigated at 600°C (1112°F), 450°C (842°F), and room temperature by metallographic and X-ray diffraction techniques. The phase relationships were found to involve only those phases present in the three binary systems. THE presence of small quantities of aluminum (approx. 0.2 wt pct*) in zinc galvanizing baths is known to suppress the formation of Zn-Fe alloy layers within the coating.' As part of an extended investigation of this suppression effect and the alloy reactions involved, the zinc-rich corner of the Zn-Fe-A1 equilibrium system containing up to 20.0 pct Fe and Al was determined at 600°C (1112°F), 450° F (842° F), and room temperature. The present paper reports the findings of this study. The constitution of the Zn-Fe system has been reported by Raynor2 based mainly on the work of Schramm3-3 and Truesdale et a1.6 The solid solubility of iron in zinc is extremely small and lies between 0.0009 and 0.0028 pct in the range 150° to 400°C (302°to752°F). Within the temperature and composition range of interest, a eutectic reaction involving nearly pure zinc, liquid = Zn+FeZn13, is observed at about 419°C (786° F) and 0.018 pct Fe along with a peritectic reaction, FeZn7+ liquid e FeZn13, at 530°C (986° F) and 6.2 pct Fe. The latter reaction is sluggish due to the large proportipn of solid phase involved in the transformation. Halla et al.,7 identified the compound FeZn13 as monoclinic with a = 13.68, b = 7.63, c = 5.07, and B = 128°44'. The structure of FeZn7 was reported by Bablik, et al.,8 to be of hexagonal symmetry, belonging to either the C6v = C6/m mc or D46h = C6/mc space group. Divensions of the unit cell are a = 12.81A and c = 57.6a. The Zn-A1 diagram as composed by Raynor9 and later Gebhardt10 is characterized by a eutectic decomposition, liquid 382°C (720°F) and 95.0 pct Zn and a eutectoid decomposition, at 275° (527°F) and 78.0 pct Zn. The eutectoid reaction cannot be suppressed permanently by quenching. Above 275° (527° F), a and a' co-exist in a closed miscibility gap between 31.6 and 78.0 pct Zn. Both phases are fcc and have nearly the same lattice parameter. The maximum solubility of aluminum in zinc (B) is approximately 1.0 pct at the eutectic temperature. PROCEDURE Materials. The experimental alloys were prepared from both massive and powdered material. Cast alloys were composed from three zinc-base master alloys containing 8.0 pct Fe, 16.0 pct Fe, and 50.0 pct Al which were made from C.P. zinc, Armco iron, and

Jan 1, 1962

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By W. E. Bruce, R. J. Morrell, James Paone

This chapter is a partial summary of an investigation by the U.S. Bureau of Mines (USBM) made in response to a recent request by the Assistant Secretary, Water and Power Development of the U.S. Department of the Interior, for a comprehensive review of horizontal boring technology related to underground power-line installation. This review is concerned primarily with 3 to 36-in. diam horizontal holes from several hundred to several thousand feet in length. An electric power system consists of three essential functions: generation, transmission, and distribution. The generation component includes the generating station and step-up substation; the transmission component includes the transmission line and stepdown substation at typical voltage levels ranging from 69 to 345 kv for underground lines and 69 to 500 kv for overhead transmission lines; the distribution component includes the distribution line carrying the commonly used voltages of 120, 208, and 240 v, the distribution transformer, and the line to the service customer.l The Federal Power Commission reports that 1600 miles of underground transmission lines of 60 to 345-kv capacity are now in service in the United States. By 1980, it is estimated that approximately 3000 miles of trans- mission lines will have to be placed underground.2 The cost of burying electric transmission lines underground in metropolitan areas, approximately 30 miles from the center of each of the most populated cities, will exceed $1.5 billion with the methods now available. The wide spread in unit costs of overhead and underground transmission lines narrows as right-of-way costs for overhead transmission in congested areas increase. Improved methods of underground emplacement will certainly reduce this difference in costs and even further favor underground emplacement. Also, in the future, overhead transmission lines will probably not be permitted in highly built-up areas.

Jan 1, 1970

By A. F. Knoll, T. Clinton Taylor

Qualitatively, galena (native lead sulfide) reacts with aqueous solutions of the xanthates,1 and has its surface sufficiently altered so that there is a tendency for air bubbles to attach themselves to the mineral crystals where there was no such effect before the treatment. This property is utilized in froth flotation operations where the mineral sulfide particles are raised into the froth and the gangue whose surface is not altered remains behind. The results of a study of this reaction were reported2 recently and certain tentative suggestions about the interaction of galena and the alkali xanthates were offered. In this paper, there is set down the results of a detailed quantitative investigation of the ions involved in this interaction with a view to finding out more about the condition existing immediately at the surface of a crystal like a heavy metal sulfide after treatment with an organic reagent. Past experimental experience showed that finely ground galena shaken with aqueous potassium xanthate abstracts xanthate ion and at the same time sulfate ion, reducing ions of the type (SmOn)= where the ratio of m to n is less than 4:l (as in sulfate), sometimes hydroxyl ion, are thrown into solution.3 Ions Involved in Xanthate-galena Interaction The present quantitative study of the galena-aqueous potassium xanthate system shows that at the lower concentrations of potassium xanthate (less than about 25 mg. per liter) the amount of xanthate ion abstracted by the galena can be accounted for by the amount of reducing ions of the (SmOn)= type and sulfate ion thrown into solution. At these

Jan 1, 1935

By AIME AIME

FRIEND recently remarked that the career of Scott Turner is characterized by Work and Wild -A Ducks. To these might be added Accomplishment and Persistent Fishing. All of these elements are manifestations of his character. The diversions-hunting and fishing-are in the nature of the proverbial trolley conductor's holiday, for many of Turner's years have been spent in the outdoors, often in distant lands, as in Spitzbergen, where the ducks pictured below were bagged. The election of Scott Turner to the presidency of the Institute marks the culmination of a quarter century of membership, during the last two years of which he has been vice-president. He was born at Lansing, Mich., on July 31, 1880, and received his A.B. at the University of Michigan in 1902, with a B.S. and E.M. at the Michigan College of Mines in 1904. Since then he has been granted two honorary degrees, D.Sc. from the Colorado School of Mines, and D.Eng. from the University of Michigan, but he still prefers to be called "Scott" rather than "Doctor." Government service was not a new experience for Turner when he was appointed Director of the U. S. Bureau of Mines by Secretary Hoover in 1925, for his first employment after graduation was as Field Assistant in the U. S. Geological Survey in Oregon and Idaho. This was followed by work in Tombstone, Ariz.; then his first foreign engagement in 1905-6 as superintendent of the San Pablo Gold Mining Co. in Panama. Various field experiences followed, though there was an interlude in work of a kind that few mining engineers ever experience. This was in technical journalism, for in 1906 he was

Jan 1, 1932

By AIME AIME

WITH a membership in the Institute of 32 years behind him, Chester Alan Fulton became an A.I.M.E. Director last month. In 1937 he served as Chairman of the Industrial Minerals Division. Mr. Fulton was born in Brooklyn on Dec. 18, 1853, and at the age of 22 graduated from the Columbia School of Mines. His first job was as assayer for the Standard Smelting Co., Rapid City, S. D., but he soon left to become shift boss in the cyanide plant of the Peregrina Mining & Milling Co., Guanajuato, Mexico. From 1908 to 1912 he was mine superintendent of the Guanajuato Mining & Milling Co., leaving there for two years of varied professional work. From 1914 to 1916 he was

Jan 1, 1939

By T. A. Rickard

A knowledge of the principles of punctuation is essential to effective and intelligible writing, for the ease and pleasure of the reader, and even his understanding, may depend upon the choice and the placing of punctuation marks. To 'punctuate' is to mark with stops or points; the word comes from the medieval Latin punctuare (punctuatus), which in turn is derived from the Latin punctum, a point. The purpose of punctuation is to show the manner in which the writing is to be understood; to indicate the relations between parts of a sentence and between successive sentences. To some extent "it does for the eye what vocal stress does for the ear", but especially it marks logical relations. Some punctuation marks, such as those indicating admiration, exclamation, and interrogation, are rhetorical as well as grammatical, but most of the common ones are logical, or grammatical. My discussion will be confined to grammatical punctuation in ordinary writing. .'The problem of punctuation in text matter", as George Summey * says, "is to employ words, points, and paragraph breaks in such a way as to achieve at the same time clearness; proper distribution of emphasis, and the desired kind of movement." The criticism of the punctuation of a sentence or of a group of sentences is not final until the context, within the paragraph, is read. A paragraph is a sentence or a group of sentences forming an independent unit of the composition; it represents a unit of thought. A multiplicity of paragraphs produces a choppy effect; 'on the other hand, paragraphs of. excessive length are tiresome, because the belaboring of one unit of thought wearies the reader. The aim should be to

Jan 1, 1931

By S. Ramachandran, R. A. Walsh

Many investigations have shown that the manganese enhances the deoxidation power of silicon. Here it is suggested that this phenomenon could be explained in terms of the formation of impure silica. Data of Hilty and Crafts on the Fe-Mn-Si-O System has been evaluated on the basis of the reaction S_i + 20 = (SiO2) where (SiO2) denotes silica of variable activity. The activity of silica in this system is a function of aMn/aSi and the temperature, and can be described by the equation 12700 l°gaSiOz = -6.85+ - - 0.5 log aMn /asi PRACTICAL melting experience has shown that it is helpful to maintain a certain range of Mn/Si ratio in deoxidizing quality alloy steels. Herty,1 as early as 1932, reported a strong association between manganese and silicon as did schenck2 and Korber and Oelsen3 in later work. More recently, Hilty and crafts4 have studied the solubility of oxygen in the Fe-Si-O system, both with and without manganese. Their study confirmed the marked ability of manganese to increase the deoxidizing power of silicon. This phenomenon has remained unexplained in the liter,ature5 since it has been shown that manganese has virtually no influence on the activity coefficients of silicon or oxygen.= In this paper, an explanation for the role of manganese is suggested and equations are devised for quantitatively describing this influence. DISCUSSION Hilty and crafts4 equilibrated their melts under an argon atmosphere and the system established equilibrium with a self-generated slag which was not always the oxide of lowest free energy. Drawing on the early work of Korber and Oelsen,3 it was reasoned that the formation of complex Fe-Mn-silicates

Jan 1, 1963

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969