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

Jan 1, 1928

The International Colloquium on Developments in Froth Flotation, which replaced the Annual University of Cape Town (UCT)/University of Stelenbosch (US) Minerals Processing Symposium, was held at the Van Riebeeck Hotel in Gordon's Bay on 3rd and 4th August, 1989. The Colloquium attracted 150 delegates from the mining, metallurgical, and chemical industries, including 9 from overseas.

Jan 1, 1989

By Nemick JA

Recent advances in computer simulation together with field measurements of caving and microseismic activity about longwall panels, has allowed a much better understanding of the caving process and the variability due to geology. The joint research between SCT Operations and CSIRO Division of Exploration and Mining has initiated new methods of computational modelling predicting various caving patterns and strata failure far ahead of the longwall face. This work was validated by field measurements of caving and microseismic activity at the longwall face.The rock fracture distribution and the caving characteristics of a range of strata sections have been simulated by computer methods. Validation studies of the method were addressed together with case studies. The interaction of caving with support convergence and face control is presented. The method allows the simulation of longwall support behaviour under various geological conditions. The system also allows a prediction of the monitoring data, which is best suited to give an early warning of weighting events or signal various key caving characteristics.

Jan 1, 1998

By J. R. Thoenen, J. D. Warne

"INTRODUCTION Red-iron-ore deposits in northeast Alabama have been exploited at vari¬ous times for nearly 6o years. About 3-1/2 million tons of ore have been produced in the Gadsden district; but mining activity has been dormant since 1926, and furnaces within this section of the State now suffer a shortage of red ore.To alleviate these shortages, work by-the Bureau of Mines was recommended after preliminary investigations. 4/5/ Diamond drilling, to determine the lateral and vertical extent of ores of known deposits in Greasy Cove and on Shinbone Ridge, was done from August 1946 to May 1947, as Project 9-106, Alabama Red Iron Ore. Three holes were drilled in each area.ASKNOWLEDGMENTSIn its program of investigation of mineral deposits, the Bureau of Mines has as its primary objective the more effective utilization of domestic mineral resources to the end that they- make the greatest possible contributions to the national security and economy. It is the policy of the Bureau to publish the facts developed by each project as soon as possible after its conclusion. The Mining Division, Lowell B. Moon, conducts preliminary examinations, does the actual investigative work, and prepares the final report. The Metallurgical Division, Oliver C. Ralston, chief, analyzes samples and makes beneficiation tests."

Jun 1, 1948

By M. A. Bérubé, M. Choquette, P. W. Godbehere

"RESUMELa scorie produite par le procédé pyrométallurgique d'extraction Noranda contient environ5% de cuivre. Elle est traitée comme un minerai conventionnel de cuivre au concentrateur de Mines Noranda et les rejets de flottation présentent encore des teneurs souvent supérieures à 0.3% en cuivre. La scorie est principalement constituée de magnétite, de fayalite et d'un verre siliceux. Bien sûr, Ie cuivre y est majoritairement sous forme de sulfures et d'un peu de cuivre métallique. Le verre contient toutefois un peu de cuivre en solution, de 0.14 à 0.33% en moyenne, selon l’echantillon examine, ce qui représente à peine 1% de tout Ie cuivre de la scorie. Dans les rejets de flottation, cela justifie par contre de 15 à 25% des pertes totales en cuivre, Ie reste se retrouvant sous forme de tres petits globules de sulfures de cuivre ou de cuivre métallique, en moyenne de 2 à 3 micromètres de diamètre et bien emprisonnes dans Ie verre.SUMMARYThe slag produced by the Noranda continuous smelting process usually contains about 5% copper. It is processed as a conventional copper ore at the concentrator of Noranda Mines. The flotation tailings still often contain more than 0.3% Cu. The slag is mainly constituted by magnetite, fayalite and a siliceous glass. Evidently, the copper occurs mostly as sulphides and, to a lesser extent, as metallic copper. However the glass contains a small amount of this metal in solution, between 0.14 and 0.33% on an average, depending upon the investigated sample. This represents scarcely 1% of the total copper in the crude slag, but as much as 15 to 25% of this metal in the flotation tailings, in which the major part of the copper occurs as very small globules of copper sulphides or metallic copper with an average diameter of about 2 to 3 um and well-locked in the glass."

Jan 1, 1987

By E. Sigal

Overview ?Intrinsik has completed several wide area HHRA and ERA studies of mining and smelting communities ?Several ?Lessons Learned? ?Key areas related to: ?Study Design ?Data Quality ?Bioaccessibility ?Speciation ?Weight-of-Evidence Approaches ?Advances in Ecological Risk Assessment Techniques

May 1, 2009

By P. Bissert, M. Klein, L. Yan, D. Yantek, R. Matetic

"U.S. Mine Safety and Health Administration (MSHA) regulations require underground coal mines to use refuge alternatives (RAs) to provide a breathable air environment for 96 hours. One of the main concerns with the use of mobile RAs is heat and humidity buildup inside the RA. The accumulation of heat and humidity can result in miners suffering heat stress or even death. MSHA regulations require that the apparent temperature in an occupied RA not exceed 95 °F. To investigate this, the U.S. National Institute for Occupational Safety and Health (NIOSH) conducted testing on a 23-person tent-type RA in its Experimental Mine in a test area that was isolated from the mine ventilation system. The test results showed that the average measured air temperature within the RA increased by 9.4 °C (17 °F) and the relative humidity approached 94 percent at the end of a 96-hour test. The test results were used to benchmark a thermal simulation model of the tested RA. The validated thermal simulation model predicted the volume-weighted average air temperature inside the RA tent at the end of 96 hours to within 0.06 °C (0.1 °F) of the average measured air temperature. IntroductionIf an accident occurs in an underground coal mine, miners who fail to escape from the mine can enter a refuge alternative (RA) for protection from adverse conditions, such as high carbon monoxide levels. One of the main concerns with the use of mobile RAs is the potentially adverse thermal environment inside an RA from the metabolic heat of the occupants and the heat released by the carbon dioxide (CO2) scrubbing system. Moreover, the humidity within the RA will increase through occupants’ respiration and perspiration, and from the chemical reaction within the CO2 scrubbing system. The accumulation of heat and humidity can result in miners suffering heat stress, heat stroke or even death."

Sep 1, 2016

By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

The metals titanium and zirconium and their alloys occupy individually unique positions in the catalogue of metallic materials available for engineering applications. Because of the uniqueness of their usage in the aerospace industry, in the case of titanium, and in the nuclear industry, in the case of zirconium, the except- ional resistance of both the metals to the majority of corrosive media is often overlooked. The cost factor in the application of these more exotic metals has, in the past, been a major considerat- ion in the rejection of titanium and zirconium as constructional materials in areas of usage where their superior corrosion resistance strongly favoured them over more conventional metals and alloys. The cost differential, vis-a-vis austenitic stainless steels, for example, is not a trifling matter, being of the order of 6 : 1, when compared on a weight basis. However, if one considers the cost, for, say, sheet product on an area basis, the ratio is redgced to approximately 3.4:1. If one also takes into account the enhanced performance of the more expensive material and the sub- sequent increase in service life and decrease in plant down-time, the economics of the usage of materials such as titanium becomes much more attractive and, indeed, highly competitive,

Jan 1, 1969

By E. A. Slover

THE usual reverberatory system of smelting cop--1- per concentrate or calcine has for its component parts a furnace and one or two waste heat boilers. These parts are operated on a basis of compromise, since the furnace can send gas to the boilers at too high a temperature and the boilers by plugging, due to dust or slag, can place a definite limit on the amount of fuel the furnace can burn. Over the years the copper concentrate smelting furnace has had few advances in design. The simple rules of design such as the flame should wipe the bath and the speed of the gases should be reasonably low for dust carrying purposes seem to cover the main features. In the construction of the individual furnaces some innovations are always being introduced. Among these are charging so that the work of smelting is a complete bath process, the use of suspended brick arches in place of sprung arches, the use of basic brick, not only in the crucible, but also in roof and sidewalls, the use of various means to feed the charge, the use of magnetite or other heavy material to construct the hearth, water cooling of bridgewall and slag skimming bay, the smelting of raw charge instead of calcine, the use of preheated air, and possibly the use of oxygen-enriched air for combustion. But the general outlines of the furnaces have not changed much except as to size. Furnaces at Hurley As shown on Fig. 1, the furnace at Hurley is 126 ft long between the longitudinal buckstays and 32 ft wide at the skewback plates. The foundation is a concrete retaining wall with piers at intervals that go deeper into the earth. Purposely the wall at the burner end of the furnace is not backed-up as tightly as the other parts of the foundation so that movement due to expansion may take place here rather than into the boiler foundations. Within these foundation retaining walls of concrete, the earth has been removed to allow the placement of the crucible brick base inside of which a silica hearth is laid 4 ft 6 in. in depth. No expansion is left in the brick base and crucible where they are in contact with the hearth. The hearth itself is of quartzite crushed to 1 in. size with fines left in the product. An 8 in. layer is laid and tamped with paving tampers to about 6 in. in thickness. Then a layer of silica flour is spread and vibrated into the hearth. This operation is repeated until a depth of 4 ft 6 in. is occupied by the silica mass onion-skinned in layers of approximately 6 in. Before firing the entire hearth is covered with broken slag to a depth of 4 in. so that a seal may be formed on the hearth. The crucible is completely faced with magnesite chemically bonded brick while the outside, against the foundation, is made of silica brick. The side-walls are carried up with silica brick in which expansion joints are left at intervals. Above the crucible the sidewall is corbelled to form a shelf on which the charge may build up along the side-walls, see Fig. 2. The arch of the furnace is sprung 20 in. silica brick, with the longitudinal centerline horizontal the length of the furnace, and some 9 ft in the center above the bath. Both straight and wedge brick are used in the construction and a thin silica mortar is troweled for joints. After the arch under heat has assumed its permanent shape, a silica slurry is spread over the arch to fill any cracks that have formed, thus giving bearing surface to the brick and preventing dust from entering the body of the arch to act as a future fluxing agent. The uptake of the furnace slopes up to the boiler entrance where a brick pilaster divides the gas stream for the two boilers. Over this flared uptake is a suspended flat arch of firebrick. The pilaster and sidewalls are constructed of firebrick but the bottom of the uptake is lined with silica brick and fettled through holes in the roof with siliceous fettling. Close to the entrance of each boiler is a brick covered slot through which water-cooled dampers may be lowered in event of boiler trouble. These water-cooled dampers are hung permanently in position ready to be lowered when needed. Flexible hoses to follow the dampers as they are lowered are connected at all times and individual chain blocks are used to lower the dampers. A pump supplying water is started before the dampers enter the heat. Charging of the furnace along the sidewalls for some 80 ft from the bridgewall is accomplished by electric vibrating conveyors fed by belt from charge storage bins above the furnace. These conveyors

Jan 1, 1954

By Knox Van Dyke, Vincent Castranova, Lixin Wu, Mark J. Reasor, James M. Antonini

"One of the proposed mechanisms involved in the pathogenesis of silicosis is that inhaled silica dust activates a ""respiratory burst"" in pulmonary phagocytes, such as macrophages and neutrophils. This increase in oxidative metabolism results in enhanced generation of reactive oxygen species which if produced in excess, would overwhelm natural defense mechanisms and cause damage to the lung parenchyma. This damage would then result in scarring, fibrosis, and decreased gas exchange.Weiss and LoBuglio' have listed several oxygen species produced by phagocytes which may be involved in cellular injury. These oxidants include superoxide anion, hydrogen, peroxide, hydroxyl radical, and hypochlorous acid. Superoxide anion (0;) is generated from molecular oxygen by the plasma membrane bound enzyme NADPH oxidase according to the following reaction:Once generated, superoxide anion can form hydrogen peroxide:In the presence of myeloperoxidase and halide, hydrogen peroxide can form hypochlorous acid:Superoxide and hydrogen peroxide can also form highly reactive hydroxyl radicals. Hydroxyl radicals can be generated slowly by the Haber-Weiss reaction:In addition. hydroxyl radical production can be catalyzed via the Fenton reaction:Hydroxyl radicals can also be generated from the reaction of superoxide and hypochlorous acid as follows:Recent investigations suggest that, in addition to the reactive oxygen species discussed above, nitric oxide may be a potential mediator of silica-induced toxicity.2-4 Nitric oxide (NO') can be generated by the cytosolic enzyme nitric oxide synthase according to the following reaction:NO synthase exists in two forms. i.e.. a constitutive. Ca2+-calmodulin-dependent form and an inducible. Ca2+-calmodulin-independent form. In pulmonary phagocytes. the activity of the constitutive form of NO synthase is low. However. NO synthase can be induced in macrophages and neutrophils by a variety of stimulants such as lipopolysaccharide. interferon y. chemotactic peptide, platelet activating factor, or leukotriene B4.3.5Once generated. nitric oxide can combine with superoxide anion to form peroxynitrite as follows:Peroxynitrite is a potent oxidizing agent. In addition, peroxynitrite can form peroxynitrous acid. which in turn can produce hydroxyl radical and nitrogen dioxide (all of which exhibit strong oxidizing potential) by the following reactions:Oxygen metabolites have been shown to cause lung damage in vivo.6 Such damage includes edema. leakiness of the alveolar endothelial/epithelial barriers, and airway constriction.7 Superoxide and hydrogen peroxide have been associated with membrane damage and cell lysis.8 These oxidants have also been associated with alteration of cytoskeletal structures at cell-cell junctions and elevation of transepithelial conductance in cultured monolayers.9 Macrophages or neutrophils can be stimulated by bacteria or phorbol myristate acetate to produce sufficient oxidant levels to lyse lymphoma cells.10 This cell killing is inhibited by catalase but is unaffected by superoxide dismutase. hydroxyl radical scavengers. or azide. i.e., an inhibitor of peroxidase. This implicates hydrogen peroxide as the active oxidant. Similarly. Weiss et al.11 have reported that hydrogen peroxide is critical in the death of cultured endothelial cells due to neutrophil activation. In addition. hydroxyl radicals generated by monocytes have been associated with cell injury.12 Lastly. peroxynitrite has been shown to oxidize sulfhydryl groups and to inactivate proteinase inhibitor making the lung more susceptible to damage caused by phagocytotic enzymes.' Therefore. a strong case can be made that activated pulmonary macrophages and neutrophils are capable of causing oxidant injury. This chapter presents in vitro and in vivo data indicating that silica is associated with the production of reactive oxygen species from these pulmonary phagocytes."

Jan 1, 1998

By Jed H. Mosgrove, Paul M. Budzak

INTRODUCTION Good mine ventilation starts at the drawing board. A coal mine will either be adequately ventilated or not, depending upon how good a job was done in the planning. Poor planning will not only result in inadequate ventilation, but may also lead to low productivity. A mine foreman cannot achieve high productivity while trying to maintain 4.2 m3/s (9000 cfm) of air at his last open crosscut. PLANNING What will provide adequate ventilation? A rule of thumb in laying out a coal mine is to provide enough entries in the main entry system to keep air velocities at 2.5 m/s (500 fpm) or less; at this rate of flow, good ventilation may be expected. The intake and return air courses of a coal mine do not improve with age. Entries will deteriorate, ribs will slough, roof will fall, and clutter will accumulate. The resistance offered to air travel will continue to increase with each passing year. Providing enough airways for the present and the future cannot be emphasized too strongly. In order to better appreciate good planning and bring it into better focus, assume a hypothetical mine has the following features: entries 1.5 m (5 ft) high and 6.1 m (20 ft) wide; one intake and one return entry; the mine development is 4.8 km (3 miles) from the intake and upcast ventilation shafts; and the ventilation requirement is 141.6 m3/s (300,000 cfm) . Air travel of 4.8 km (3 miles) into a mine and the same distance back to the fan is not unusual. However, to do so with one intake and one

Jan 1, 1981

By J. Dean Warner

In 1984, as part of a project to evaluate Alaskan occurrences of certain critical and strategic minerals, the Bureau of Mines investigated a columbium-bearing regolith on upper Idaho Gulch, near Tofty, AK. The regolith is derived from weathering of a dolomitic marble and consists mostly of iron oxide minerals with accessory apatite, zircon, xenotime, rutile, monazite, and the columbium minerals aeschynite, columbite, and ilmenorutile. Two regolith lenses contain 340,000 lb of columbium resources at an average grade of 0.07 pct. Calculated composite concentrates from two regolith samples (approximately 200 lb each) contained 53 and 57 pct of the columbium at grades of 0.97 and 0.86 pct, respectively. In each case the grade could be improved to 1.1 pct Cb with a sacrifice of 9-pct recovery. The regolith's mineralogy, trace-element geochemistry, and similarity to descriptions of other columbium-enriched regoliths suggest that the underlying marble may be a carbonatite. The lack of associated alkalic igneous rocks and the stratiform nature of the regolith, however, may be interpreted as evidence for sedimentary origin of the marble. The marble and regolith are a lode source for some of the minerals in the Idaho Gulch placer deposit.

Jan 1, 1986

By Hans-Christian Kurzweil, Klaus Mussger

CERN, the European Laboratory for Particle Physics, are upgrading their existing particle accelerator for the next generation of experiments and have three major packages of underground construction work in progress. Each package involves the construction of shafts, cavern, tunnels and surface buildings. This paper gives an overview of CERN, the LHC Project and a more detailed discussion of design process, design review and construction works of Experimental Point 5. The LHC works at Point 5 include two large shafts, two major parallel caverns with a total span of 50 m, which are separated by a 7 m wide and 28 m high concrete pillar, and a system of secondary tunnels and caverns. The overburden ground consists of around 50 m of water bearing moraine (silty, clayey gravels and sands) overlying 20 mof molasse, which consists of horizontally bedded marls and sandstones. The shaft shave been constructed with ground freezing, primary concrete lining, membrane and secondary slip formed concrete lining. The concrete pillar was then excavated and concreted in advance of excavation of the two caverns. Cavern construction includes primary support of shotcrete lining and rock bolts, followed by waterproof membrane and primary support of shotcrete lining and rock bolts, followed by water proof membrane and insitu concrete secondary lining.

Jan 1, 2003

By Norman Ketzlach

Manganese Products, Inc. has developed a chemical process for the recovery of high-grade manganese oxides from low-grade manganese ores. Ammonium sulphate is also produced. Manganese ore is leached with sulphurous-sulphuric acids. The impurities are removed with ammonia, heat, and air. Manganese oxides are produced by addition of more ammonia and air under pressure. Ammonium sulphate is recovered from the remaining solution.

Jan 3, 1950

By B. G. H. Thomas, W. P. Yant, A. C. Fieldner, R. R. Sayers, W. J. McConnell

"One of the outstanding problems confronting automotive engineers in attempting to construct motors of greater economy is that of eliminating the ""knock"" from the operation of the engine. Recent investigations of this detonation or knock in internal-combustion engines, especially of the high-compression type, have demonstrated that it can be eliminated or reduced by decreasing the reaction velocity of combustion by adding small quantities of certain compounds to the gasoline, This makes it possible to use engines of a higher compression ratio, thereby greatly increasing the mileage per gallon of gasoline consumed. The savings in fuel reserves from increasing the proportion of crude oil marketable as motor fuel and in permitting the designing of more efficient engines are obvious.Ethyl gasoline, one of the widely used anti-knock fuels, is ordinary motor gasoline to which has been added 3 c.c. of tetraethyl lead and 2 c.c. of a halogen carrier, as ethylene dibromide or trichiorethylene, or approximately 0.06 per cent of the lead compound and 0.04 per cent of ethylene dibromide by volume. Ethyl gasoline should not be confused with ethyl fluid, which is a mixture of concentrated tetraethyl lead and ethylene dibromide in the prowler proportions for mixing with gasoline, but is not a motor fuel and is not sold to the public. Also tetraethyl lead is not a motor fuel, and likewise is act sold to the public."

Dec 1, 1924

By Joseph M. Kurtak

The U.S Bureau of Mines conducted a five-year mineral resource assessment of the 16.6 million acre Colville Mining District in northern Alaska, which includes part of the National Petroleum Reserve in Alaska. The study was initiated at the request of the Bureau of Land Management, which administers the majority of the region. The study was done in cooperation with the Alaskan Division of Geological and Geophysical Surveys, the U. S. Geological Survey, and the University of Alaska. During fieldwork, 1593 rock, soil, and stream sediment samples were collected and four bulk samples taken for beneficiation studies. A total of 40 mineral occurrences were documented, including 27 which were previously undescribed. No mining has occurred within the district. Mississippian carbonaceous shale and siliceous mudstone contain stratiform exhalative lead-zinc-silver occurrences. Grades average 8.0% combined lead/zinc and 51 gm/mt silver. Upper Devonian to Lower Mississippian sandstones host breccia veins, containing up to 29% combined lead/zinc and 274 gm/mt silver. Mineralized quartzites of similar age have potential for disseminated-type lead-zinc deposits. Samples from Lower Cretaceous mudstone and shale beds up to 6.5 meters thick, contain as much up to 12% manganese. Upper Mississippian carbonaceous shale and limestone beds contain up to 23% phosphate. Stratiform barite deposits hosted by cherts, are up to 27 meters thick with an average specific gravity of 4.16. Vein-type fluorite occurrences are associated with Mississippian limestone. Moderate potential exists for development of zinc -lead-silver, barite, and phosphate deposits.

Jan 1, 2011

By Edgar J. Briceño

El presente texto señala el resultado de algunas pruebas realizadas en el período de 1974 y 1979 en la concentradora de Toquepala, a fin de mejorar el proceso de producción en la industria minera. Para ello, se ejecutaron 14 pruebas a nivel de planta, de donde se seleccionaron seis, las cuales se ejecutaron también a nivel de laboratorio para así compararlas con lo standard. Las seis pruebas referidas son: Evaluación de forros de jebe en molienda, evaluación de diferentes tamaños de bolas, evaluación del espumante Celaproht-16, efectos de Asmol Polhalla m- 59 en sedimentación y filtrado de las colas de planta de Molibdenita, evaluación del espumante Ucon R-23 y lonas tampereen en el filtrado,

Oct 14, 1980

By Carol A. Hill

Native sulfur occurs with barite, celestite, and bioepigenetic calcite in the Culberson, Pokorny , and Leonard Minerals deposits, Delaware basin. The sulfur in these deposits, in "castile" masses, and in deposits of the Fort S tockton district have 6 34s values between +9 and -15. Native sulfur in the caves of the Guadalupe Mountains is somewhat lighter [(634s = -15 to -25)]. Barite in the Culberson, Leonard Minerals, and Comanche Creek sulfur deposits have 63% values of +35 to +73; celestite in the Culberson and Leonard Minerals occurrences have values of +38 and +36, respectively, and 87Sr/86Sr values of 0.707808 and 0.708138, respectively. Barite associated with sulfide, deposits, Guadalupe Mountains, have [634s] values of +41 to +62. Barite at Seven aeart Gap, Apache Mountains, is somewhat less enriched in heavy sulfur [(634s = +14 to +37)].

Jan 1, 1992

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965