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By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.' The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.' The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,' since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By John R. Green

Rotary kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary accorcling to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. Measurements of Kiln Temperature The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records ox automatic control are desired, while Optica1 pyometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. 1 shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected From puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0" to over zoo°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1942

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sigurdson

CONSIDERABLE uncertainty is revealed in the literature regarding the nature of the titanium minerals which make up the bulk of the heavy, opaque fractions of numerous beach sand deposits of the world. An investigation was made, therefore, of beach sand concentrates of North Carolina, Florida, Brazil, and India. Magnetic concentration, X-ray, and microscope data were obtained which show that these concentrates consist essentially of ilmenite and its alteration products. The alteration, brought about by oxidation and leaching of iron values, has resulted in upgrading the ores to a range of 56 to 64 pct TiO2, as compared with 52.7 pct in ilmenite of theoretical composition. Conclusions drawn regarding the nature of the dominant titanium-bearing mineral in beach sand deposits have been based mainly on chemical composition, specific gravity, and petrography. This material has usually been referred to as ilmenite or weathered ilmenite. It has also been referred to as arizonite because in chemical composition it resembles an occurrence in Arizona which was described by Palmer1 in 1909.

Jan 8, 1954

By J. J. Beeson

Page I. PrimaRy MineRalization............................................ 356 1. Introduction..................................................... 356 a. Scope of Work............................................... 356 6. Acknowledgments............................................ 357 c. The Bingham Mining District.................................. 357 d. General Geology.............................................. 357 e. The Utah Copper Mine....................................... 376 f. Field and Laboratory work.................................... 376 2. The Quartz-Monzonite.............................................. 377 3. The Pegmatite Veins.....:.•..............................:........ 378 4. The High-Temperiture Veins.........................-.............:379 5. The Early Hydrotherma! Period.:......................'............ 380 6. The Late Hydrothermal Period................................:.... 385 II. Seconuabx EnricuMENT............................................. 386 . 1. Author's Note;..... ;............................................ 386 2. Factors Governing Enrichment.....................................: 387 3. The Enrichment.................................................... 387 4. The Covellite Enrichment.; .:; ; : .:. :..:.............:................ 388 a. The Capping above the Covellite Ores:....:....................... 388 b. Conclusions Drawn. from a Study of the Capping and the Covellite ; Ores....,.............................................:.....,.' 392 c. Covellite Enrichment at Depth......:......................... : : 392 5. The Chalcocite Enrichment...................................... ; 394 a. The Carbonates in the Capping above .the Chalcocite Ores...:..: .. 394 ' b. The Formation of Chalcocite..:.:. :......:..'...........,......' 394 . 6. Secondary Chalcopyrite and Bornite.............................i ..., . 395 111.- Conclusions as to the Formation.oF the ImpoRtant Sulphides in the Disseminated ORes........................................,.......... 400 I. Primary MiNeRalization 1. Intrdtiction a. Scop. e .of Work.. first part bf, this paper deals with the country rock, its pegihatitic, pneumatolytic', and hydrothermal altektions; also, the effect of magnetite on the deposition of the primary chalcopyrite and pyrite.

Jan 1, 1916

By Arthur F. Wendt

Introduction.—In the year 1885, the writer signed a contract to take charge of the reopening and developing of the celebrated old mines of " El Cerro Rico de Potosi." Two years earlier, an Eng- . lish firm of engineers had made a very glowing report on the property. In the summer of 1885, telegrams arrived from the parties in charge of operations at the mountain, claiming the finding of one of the old veins, with an average richness of over 200 ounces to the ton. In the fall of 1886, the author first personally visited Potosi, but found neither the English report nor the telegram borne out by the facts. After an expenditure of over half a million of dollars and more than three years of continuons hard work, the writer succeeded in unwatering and developing one of the principal old veins of the mountain. This vein, called "Cotamitos," now yields ores of about 75 ounces to the ton, and the old historic mountains of Potosi may be said to have again fairly entered the list of silver-producers. The experience of the author, during his residence in Bolivia, and data obtained from Sr. Don F. Avelino Aramayo, form the basis of this description. POTOSI. Etymology of the Name.—The Quichuá (pronounced Keechna) Indians, known to North American students as the " Incas," although the word "inca" merely signifies ''king," or "chief," of the Quichuás, called the mountain "Sumac-orcko," or the beautiful mountain." Eighty-three years before the discovery of the mountain by the Spaniards, the inca, or king, Huaina Ccapac, travelling from Cantumarca to Calque-Porco, saw the mountain of Potosf and, admiring its grandeur and beauty, said that within its bowels there was, no doubt, much silver. He ordered his vassal* to work the mines. They, having carried their mining implements to the mountain, ascended it and were on the point of commencing work, when they heard a voice of thunder, which said: " Do not take

Jan 1, 1891

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By George E. Thackray

In December, 1894, the Cambria Iron Company made a number of heats of Bessemer steel to be used in structures by one of its customers, subject to inspection and tests by a firm of consulting engineers, one of the requirements being that the material should riot exceed .08 per cent. of phosphorus. In other respects the requirements were such that they could only be met by material of good quality; but the general spe cification is not introduced here, as it is not the purpose of this paper to deal with anything except certain difficulties encoun tered in determining the phosphorus-content of the material in a manner satisfactory to both seller and buyer. Preliminary determinations of phosphorus were made in sample-ingots from each of the heats from which material was rolled for the order in question, and these preliminary chemical tests, made in the laboratory of the Cambria Iron Company, showed that, with very few exceptions, every heat was within the prescribed limit of phosphorus. After the material had been rolled, sample-drilling8 of finished material were taken from the various heats in the regular manner in use at the works, these samples being thoroughly mixed and divided into two parts, one of which was analyzed at the works' laboratory and the other sent to the inspecting engineer. Several hundred determinations were made from this mate rial without reaching an agreement between the work of the inspector's chemist and that of the works' chemist; but as it is not the object of this memorandum to treat of this part of the subject at length, it is considered sufficient to present herewith only a few of these first determinations. The analyses given in Table I. are those of the original series made on the heats which were afterwards resampled for final determination by an arbitrator; and they are selected for this reason, as the entire " comparison is thus rendered more complete.

Jan 1, 1896

By G. J. W. Kor, F. D. Richardson

The sulfide capacities a1 1500°C of slags in the systern CaO + CaF, +Al2O3 have been measured by bringing samples into equilibrium with gas mixtures made from CO + CO2 + SO, + N2. The capacities are negligzble both JOY CaF, and CaF, + Al2O3 melts but when lime is present even at 20 wt pct capacilies as high as 30 x lom3 can be obtained. The results have yielded information concerning the liquidus at 1500°C and fluoride-oxide melts in general. The slags used in electroslag refining contain substantial amounts of calcium fluoride. Robinson and Grainger' report that good results can be obtained by using slags of the approximate composition 70 wt pct CaF2 + 30 pct Al2O3. It has also been reported2 that a mixture of 50 pct CaF2 + 30 pct A12O3 + 20 pct CaO makes a good slag for general use. In view of the fact that very low sulfur contents are claimed for ingots produced by the electroslag process. studies have been made of the sulfide capacities [c, = wt pct S (PO2/Ps2)1/2 at 1500°C. of slags consisting of pure calcium fluoride, and of its mixtures with lime and/or alumina. These studies have also provided information on the phase diagrams. The slags were brought into equilibrium with gas mixtures prepared from NZ + CO + CO2 + SO2. Because CaFz is volatile and also easily hydrolyzed. measurements were made of its loss in weight in various flowing gas mixtures. EXPERIMENTAL Procedure. The apparatus and procedure were the same as described previously. Both platinum and iridium crucibles were used (height and inner diameter about 1 cm), but those made from iridium were stronger and able to withstand a greater number of experiments. In each experiment two crucibles were set in an alumina support and 1 g of slag mixture was divided between them. The materials from each crucible were analyzed separately after being brought to equilibrium with the gas, and then quenched in the water-cooled end of the reaction tube. Materials. Alumina and lime were prepared as de-scribed previously.4 Calcium fluoride was obtained by igniting Analar calcium fluoride in a platinum boat at about 800°C in a stream of pure dry nitrogen: the product was cooled in a desiccator. The slags were produced from mixtures of the powdered constituents, these being melted together in the course of each equilibrium experiment. The sulfur analyses and the X-ray diffraction meas- urements on the solidified slags were made as described previously.4 From the latter it appears that the CaF2 contained less than 0.5 mol pct CaO. RESULTS Values of (ps2/po2) for the Gas Mixtures. The re-sults have been represented in terms of (ps, /Po,)"? for the various gas mixtures used. The va1;es of this function at 1500°C are listed in Table I: they were calculated from the data cited previously for calculations at 1350°C 4 Weight Losses with CaF, and CaF, + CaO. The re-sults of the weight loss measurements* at 1500°C for

Jan 1, 1970

By R. S. Handy

The No. 2 unit of the West Mill of the Bunker Hill & Sullivan Mining & Concentrating Co., which went into commission Apr. 17, 1912, is structurally a twin of the No. 1 unit, which was started Nov. 9, 1909. Up to the point where the ore enters the concentrating-de-partment, it follows precisely the process described by G. Cae-tani in his article entitled, Milling of Lead-Silver Ores,' under the heading, Preparation of the Mill-Ore. The process from this point forward, in the No. 2 section, is outlined on the accompanying flow-sheet. In describing it I shall attempt to analyze the products of each separate process. The constancy of the tonnage and the uniformity of the quality of the feed render this practicable. No. 1.—550 tons of feed, all having passed 30 mm., is washed into two 15-mm. trommels, 4 ft, in diameter, 60 in. long, 17 rev. per min., 1 in. slope, 3/8-in. gauge steel.

Jan 1, 1913

By W. M. Small

Austria.—Austria produced some 430 cisterns of 10,000 kg. each of crude oil of a 0.9428 sp. gr. during 1934. Gosting II well near Zis-tersdorf was placed on the pump in August and at the end of the year was still producing about three cisterns daily. This well is owned by the Erdöl-Produktionsgesellschaft while Gösting I is owned by Raky-Danubia. Only five wells were completed in the republic during the year. These accounted for 1783.5 meters of the 2225 meters drilled. The only producer completed was Gosting 11. At the close of the year, four rigs were in operation and one rigging up. At least 8 or 10 new wells are planned in Lower Austria for 1935. The European Gas & Electric Co. put its 6-km. gas line into operation in May and has sold 12,301,550 cu. m. of gas to the Vienna City Electric Works. A 2-km. pipe line was built from Gösting II to the railway loading rack near Zistersdorf. Hungary.—No oil or gas was produced except a small amount of gas trapped from flowing artesian wells. The Government completed and abandoned a 1500-m. hole at Tisztaberek in northeastern Hungary and is drilling at 967 m. near Bogáes, 120 km. northeast of Budapest. It is unofficially reported it plans to drill two new wells in 1935. The European Gas & Electric Co. has a rig up for a test at Mihalyi in Transdanubia. Czechoslovakia.—In Gbely (Egbell) there were produced 1283 cisterns of 10,000 kg. of 0.935 sp. gr. oil and a small amount of gas used for fuel. This field is operated by the Government; 17 shallow producing wells and three dry holes were drilled, with a total of 3351 m. of hole completed. In Hodonin (Goding) there were produced approximately 1300 cisterns of 10,000 kg. each of 0.91 sp. gr. oil and a small amount of gas used for fuel. The field is operated by the Apollo, which drilled four producing wells averaging 460 m. in depth, one small gas well of 550 m., one small gas well 260, and one dry hole 230 m. Two wells were deepened a total of 80 meters. The Government is drilling below 800 m. in a wildcat test in eastern Czechoslovakia near the Rumanian frontier.

Jan 1, 1935

By Hallan Marsh

THE subject of this paper is apt to bring to mind wells ranging from 6000 to over 8000 ft. in depth. However, it is uncommon to pump wells at depths greater than about 5000 ft. Fig. 1 shows the number of wells being pumped at various depths by one company in Southern California. FIG. 1.-NUMBER OF WELLS BEING PUMPED BY ONE COMPANY FROM VARIOUS DEPTHS IN SOUTHERN CALIFORNIA. A few companies have a very few wells pumping at depths greater than this. This paper will deal with wells between 3000 and 5500 ft. in depth. Most California oils at these depths are between 25° and 35 gravity. The subject is so broad that it will be necessary to omit many interesting phases, and to treat others very briefly. Power, power transmission equipment, power efficiency, counterbalancing, sucker rods, pumps and volumetric efficiency will be discussed.

Jan 1, 1928

THIS method of melting with a little wind furnace is called by many melting with air. It is a method that is done with little labor. First a furnace is made with crucibles and charcoal. It is small or large as you wish, without blast from bellows, but not without a draft of air which proceeds from the place where it is made and from the arrangement of the furnace.* This, after a certain period of time, has the effect of melt- [ ] gin the thing in the quantity that you wish, provided, however, that you proportion it properly to the space, to the fire, and to the air which makes the wind. In order to make this, the aforesaid furnace is first made of bricks, or it is dug out of an elevation of stone or [106V] in a wall of clay. It can also be made portable with iron bars and loam as I shall tell you. However you may make it, you must place it in a spot that is windy, for instance, in some large room or opposite doors or windows. It is made round or square as is most pleasing to him who is to make it. But here we will now say that it is to be made square for greater convenience of building with bricks. Having chosen the place, make it a half

Jan 1, 1942

NEW MEMBERS The following list comprises the names of those persons who became members during the period of July 10, 1917, to Aug. 10, 1917. ARNOT, STANLEY L., Engr., Plymouth Cons. Gold Mines; Ltd., Plymouth, Amador Co .2 Cal. BARRETT, LESLIE PARK, Asst. Geol.... Michigan Geological Survey, Lansing, Mich. BENNIE, JOHN WILLIS Gen'l. Mgr., Shannon Copper Co., Clifton, Ariz. BRINTON, OWEN FUGATE Mgr., Admiralty Zinc Co., Quapaw, Okla. BRODERMANN, JORGE, Civil Engr., Compania Minera San Francisco, Havana,Cuba. BROWN, RICHARD HENRY JR., Sales Engr., Ingersoll Rand Co., 300 N. Broadway, St. Louis, Mo. BROWN, STANLEY Chile Exploration Co., Chuquicamata, Chile. BUDDECKE, WILLIAM A Pres., Point Milling & Mfg., Co. Mineral Point, Mo. BURGESS, GEORGE K., Physicist and Chief, Division of Metallurgy, Bureau of Standards, Washington, D. C.

Jan 9, 1917

By Kefton H. Teague

Olivine is a mineral containing a mixture of forsterite (Mg,SiO,) and fayalite (Fe,SiO,) in solid solution. The name "olivine" was first applied by Werner in 1790 (Hunter, 1941) because of the olive-green color of the mineral. Uses The principal use of olivine is in various foundry applications. Perhaps the largest tonnage is utilized as a special foundry sand for mold-making in brass, aluminum, and magnesium foundries (Schaller, 1957, 1958; Snyder, 1957). Olivine was first used as an industrial mineral in the early 1930s for a refractory material (Anon., 1970; Hunter, 1941). As a refractory raw material, olivine was first introduced in the United States as handcobbed, selected, shaped blocks of crude olivine. This use met with limited success. More recently, finely ground olivine blended with MgO and pressed into bricks, which are then fired, have found use in glass tank furnaces and open-hearth furnaces. Ramming or gunning mixes for basic furnace linings also utilize olivine. Olivine has been used in ladle linings with varied success. In Europe, substantial tonnages of olivine are utilized in refractory brick for night storage heaters (Anon., 1970). A limited amount of olivine has been used in the past as a fertilizer (magnesium source) and has been fused with rock phosphate to produce a magnesium phosphate as a plant food. The relatively high magnesia (MgO) content of olivine also attracted attention to it as a potential source of both magnesium compounds and as a source of metallic magnesium (Bengston, 1956; Hunter, 1941). Industries using olivine have not standardized specifications. Normally, producers supply a product which meets individual customer requirements. Such requirements involve type and amount of impurities, grain size of product, refractory characteristics, etc. Geology Olivine occurs commonly as accessories in basic igneous and basic metamorphic rocks. Economic deposits are of magmatic origin and are restricted to essentially the dunite variety of periodotite. Dunites are medium to coarse- grained crystalline rocks, generally reddish brown on weathered outcrop, and are composed primarily of olivine.

Jan 1, 1975

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

H. M. HOWE, Bedford Hills, N. Y.-One wonders, whether it might not be well to check, by a rather simple and direct way, the inferences that would be drawn from this investigation. Suppose we quench, in these various liquids cylinders of steel, selecting material that is not likely to split in hardening, and then examine their cross-sections micro-scopically. If the cylinder is of any size, you will find a series of concentric bands, a very hard band, a softer band, and a hard band-but it seems that here would be a way of checking the inferences from the cooling curves by comparing these waves of hardness obtained in similar speci-mens quenched in different liquids. One would think that there would be great promise in that way. One's first thought is to quench similar pieces of steel, similarly heated, in different liquids and determine their hardness. I suppose many of us have tried that. We then meet the-difficulty that it is not the most rapid cooling that gives the greatest hardness. There is an intermediate rate of cooling that gives maximum hardness so that you can not by any simple method as that check this cooling method. But it seems possible

Jan 12, 1919

Illinois is rightly known as containing the coal deposit of which the first record in the United States was made. Joliet and Marquette saw "charbon de terre" along the Illinois River in 1673;1 LaSalle saw "mines de charbon" along the same stream in 1679; and Hennepin reported having "found in Several Places Some Pit-Coal" in 1682.2 In 1687 Jontel, in writing of the Illinois River country said, "along the river are coal pits, the coal whereof has been try'd and found very good."3 J. Carver reported the northern parts of the Mississippi River valley, "containing lead, copper, iron, coals, etc." in 17664 evidently referring to the Illinois country. Croghan, in the same year, saw coal along the Wabash River, near the mouth of the Vermilion in Indiana, but not far from Danville. Capt. Philip Pittman in his journey up the Mississippi in 1770 reported that "great pieces of coal are constantly found on the sand-banks, from whence it may be concluded, that there are coal-mines on the upper parts of the Mississipppi."5 This coal could only have come from the Illinois or Big Muddy Rivers. Morse, in 1798, refers to great quantities of coal on the upper branches of "the Father of Waters," and "on the Illinois River is a coal mine, which extends for half a mile along the middle of its banks."6 While, undoubtedly, some coal was used locally in various places, no records have been left of it and the first definite one is that in 1809 William Boon shipped some coal from the Big Muddy River, in Jackson County, to New Orleans, which was the first coal exported from Illinois.1 There has been considerable discussion as to this first shipment, whether it was made in 1809, 1810 or 1812. The records of arrivals of: boats in New Orleans in those early years is specific as to date, name of craft and name of captain, but no mention is made of cargo carried. William Boon arrived

Jan 1, 1942

By Roy R. Jones, R. R. Sawyers

It has long been comnlon knowledge that workers in anthracite are prone to develop a disabling disease of the lungs. Some of the earliest scientific contributors dealing with anthracosis were: Pearson1, in his report in 1813, on the coloring matter of the bronchial glands and black spots in the lungs; Stratton2, in 1838, who first termed the condition anthracosis; Greenhow3, who reported to the pathological society in 1865, on the Black Lung of the Collier, and Pick4 in 1870, who reported on the chemical composition of the ash of a collier's lungs. Visconti5, in 1870, is accredited with being the first to use the term "silicosis" to denote the pathological condition of the lungs resulting from the inhalation of silica. Rovida6 confirmed the reports of Pick and Visconti in 1871, in his report on a case of silicosis and chemical examination of the lungs for silica content. The relationship of pulmonary infection, as associated with disabling pneumoconiosis affecting the coal miner, has frequently been discussed. While most reports have emphasized the role of infection, there has been some disagreement regarding the prevalence of tuberculosis among those suffering from anthracosis. The report by Wainwright and Nichols7 in 1905 has frequently been cited to show that the incidence of pulmonary tuberculosis among coal miners was less than that among the general population. It was their opinion that pulmonary tuberculosis was more prevalent among the miners' families than among the miners themselves. Collis and Gil-christ, in 1928 in their study of the Effects of Dust upon Coal Trimmers, concluded that among such workers there was an excess of deaths from bronchitis and pneumonia but not from pulmonary tuberculosis. They

Jan 1, 1936

By Klaus Emicke

The paper describes the lead refining process operated at Norddeutsche Affinerie (N.A.). Incoming materials are different grades of lead with varying percentages of impurities: Cu, Te, As, Sn, Sb, Bi, precious metals. The facilities are designed for charge-wise operation. After drossing, generally Te, As, Sn and Sb are removed substantially by the Harris Refining Process using fused NaOH. A certain selectivity during refining is achieved by controlled addition of NaNO3. Another refining step is decopperizing by means of elemental sulfur. Complete separation of Te, As, Sn and Sb is accomplished by chemical methods in a leaching plant. A Howard Press is used in the Parkes Process for desilverizing. After vacuum dezinking in kettle, Bi is removed, if required, by means of Ca and Mg. In an end refining step Ca, Mg and Zn are removed by having the lead melt treated with NaOH and NaN03. The refined lead as such, or in the form of special alloys, is cast by an ingot casting machine into 50-kg ingots. Zinc which is used as a precipitant in the Parkes Process is recovered by distillation from the high grade Ag-Zn-Pb crystals in Faber du Faur retorts while the Pb/Ag alloy is fed to the cupellation furnace. Ca and Mg are removed from the Ca-Mg-Bi crystals formed in the course of Bi removal, and the Bi-bearing lead is cast into anodes. The electrolytic lead refining facilities at N.A. are operated largely for the purpose of separating Pb and Bi. These facilities are also used particularly for the refining of Bi-bearing lead which had gone through the above process, but from which Bi has not been removed by Ca and Mg.

Jan 1, 1970

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970