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By Nobuaki Sato, Tetsuo Fukasawa, Akira Kirishima

To apply the fluoride volatility process for the treatment of fuel debris formed in the damaged nuclear reactors, study on the fluorination behavior of main constituents, such as fuel and cladding is essential. The mixture of uranium and zirconium oxides is formed under severe conditions such as high temperature and oxidizing atmospheres. In this paper, fluorination and volatilization behavior of uranium and zirconium oxides have been studied by TG-DTA method in the presence of fluorine. From the TG-DTA result of UO2 in F2 atmosphere, the weight gradually increased up to 7% at 350 oC followed by rapid weight decrease with exothermic peak showing the vaporization of uranium as UF6. ZrO2 showed similar fluorination behavior to that of UO2. However, fluorination of UO2-ZrO2 seemed to be suppressed with increasing ZrO2 amount. This may be caused by the formation of solid solution.

Jan 1, 2016

By H. G. Wickes

Virtually all fluorine consumed by the aluminum industry is as the electrolyte of the Hall-Heroult process for producing primary aluminum. A small amount of fluorspar is used but most fluorine is consumed as either aluminum fluoride or cryolite. Some fluorine- containing materials are used in secondary aluminum production, but the amount is negligible compared with primary production requirements. Any analysis of the future of the primary aluminum industry must take into account two powerful and closely related driving forces which are shaping that future. These factors are increasingly stringent restrictions on the emission of pollutants and the continuing cost-price squeeze. Nowhere do these factors combine more forcefully than in the area of fluorine consumption. We can safely assume that industry efforts to reduce fluorine consumption will be intensified and that these efforts will be fruitful. This paper will attempt to identify and quantify the factors and trends of fluorine consumption during the next decade. We will be concerned primarily with the demand for new fluorine. Sources of new fluorine will not be treated.

Jan 1, 1973

By Haskiel R. Shell

While the original purpose of the Bureau of Mines work on fluorine micas was to synthesize large single crystals or film suitable to replace natural muscovite or phlogopite, the objective was broadened to include development of the many possible fluorine micas as a class of new, unique materials. Several methods were developed for the synthesis of the fluorine micas at atmospheric pressure: Solid state reaction, melting in crucibles, internal resistance electric melting, and arc resistance electric melting. The latter two methods are now med commercially. A variety of fluoromicas were synthesized by isomorphic substitution including disilicic, trisilicic, and tetrasilicic. Fluorophlogopite, KMg3AlSi3O10F2, is the fluoromica most widely used. While most of the fluoromicas are completely stable to water, many water-swelling fluoromicas and fluoromontmorrilonoids were synthesized. Single crystals or film of the fluorine micas were grown to 2 inches or more by a number of methods, but none has as yet proved economical. In the report, detailed data and descriptions are given on compositions, syntheses, products, and uses, and on the properties including physical, dielectric, chemical, X-ray, optical, and structural.

Jan 1, 1969

By J W. Glatthaar, M Mavotoi

The occurrence of fluorine in the copper/gold concentrates produced by Ok Tedi Mining Limited has provided a series of challenges to metallurgists since 1988. Although fluorine is distributed throughout the gangue minerals contained within Ok Tedi ores, itsÆ presence in talc and phlogopite (naturally floating fluorosilicates) has proven to be the predominate sources of fluorine in the final concentrate. Initial treatment for the fluorosilicates consisted of the use of a carboxy-methyl cellulose depressant added to the flotation cleaners. This was superceded in 1998 with the installation of a fluorine reverse flotation process for the removal of naturally floating fluorosilicates from the final concentrate when the fluorine content of the final concentrate exceeds smelter-defined trigger points. The fluorine reverse process is similar to by-product molybdenite concentrate production in that sodium hydrosulfide is used to depress copper/gold flotation whilst allowing the fluorosilicates to float. The process was installed in two parallel modules (to match the existing grinding/flotation modules at Ok Tedi), each consisting of a closed rougher/cleaner circuit configuration. Both rougher and cleaner cells are Jameson Cells from MIM Process Technologies, with the selection based on both processing characteristics and available construction space. This paper discusses both the nature of fluorine in-, and its removal from-, Ok Tedi copper/gold concentrates.

Jan 1, 2003

By P. L. Crouse

"SynopsisFluorine – in the form of hydrofluoric acid, anhydrous hydrogen fluoride, elemental gaseous fluorine, fluoropolymers, volatile inorganic fluorides, and more – has played, and still plays, a major role in the nuclear industry. In order to enrich uranium, the metal has to be in the gaseous state. While more exotic methods are known, the standard and most cost-competitive way of achieving this is by means of uranium hexafluoride (UF6). This compound sublimates at low temperatures, and the vapour is enriched using centrifugal processes. The industrial preparation of uranium hexafluoride requires both elemental fluorine gas and anhydrous hydrogen fluoride (HF). HF is prepared by the reaction of sulphuric acid with fluorspar (CaF2). Fluorine gas in turn is prepared by the electrolysis of HF. Yellowcake is first converted to uranium tetrafluoride (UF4), using HF, after which the compound is treated with fluorine to yield UF6. After enrichment, the UF6 is reduced to UO2 for use in fuel elements in pellet form.South Africa has the largest reserves of fluorspar internationally, and is the third largest producer after Mexico and China. Fluorine technology has many associated difficulties, because of the reactivity of fluorine and the toxicity of HF. The main barriers to entry into the fluorochemical industry are thus the abilities to produce both HF and F2. Both these substances are produced locally, at the industrial scale, at Pelchem SOC Ltd. Should South Africa contemplate developing its own nuclear fuel cycle as part of the awaited new-build nuclear project, it will be imperative to leverage the existing skills with respect to fluorine technology, resident at both Pelchem and Necsa, for this purpose. This paper summarizes the fluorochemical skills developed locally over the past several decades, and suggests strategies for maintaining the technology base and developing it for the next generation of scientists and engineers.IntroductionFluorine chemistry has always had a very close relationship with the nuclear industry. Although the first mention of fluorspar was recorded in the sixteenth century, and the fundamentals had been well-developed by the Second World War, it was only during the Manhattan Project (Banks et al., 1994), when almost unlimited funds were made available for the large-scale industrialization of fluorine and related compounds, that the technology took off. Expertise in both the chemistry and the engineering aspects of fluorine is essential for the design and running of several of the unit processes in the nuclear fuel cycle."

Jan 1, 2015

By S. L. Weber, V. Castranova, D. E. Banks, J. K. H. Ma, Y. Rojanasakul, J. Y. C. Ma, M. Bhat

"The mechanism of bleomycin-induced pulmonary fibrosis is not ye: clear. Recent studies have shown that alveolar macrophages (AM) can be stimulated by bleomycin in vitro releasing inflammatory cytokines, suggesting that the interaction of bleomycin with AM is an important step in the drug-induced fibrotic process. Bleomycin is known to bind DNA and generate oxygen radicals through complexation with Fe2+ and oxygen. To provide,more insight into the cellular oxidative property of bleomycin, v.s have developed a fluoromicroscopic method using 2',7'-dichlorofluorescin diacetate (DCFHDA) as an oxidative fluorescence probe to study the deomycin-induced intracellular oxidation in rat AM and the inhibition of the oxida¬tion by taurine, a compound known to inhibit the bleomycin-induced fibrosis. Bleomycin at 5 to 20 ug/ml has a moderate stimulatory effect (1.87- to 2.66-fold) on the secretion of superoxide anion. A high concentration of bleomycin (20 ug/ml), however, inhibits cell response to zymosan-induced secretion of superoxide anion. At 4 ug/ml, bleomycin has no effect on cell membrane integrity or morphology but results in a significant increase in intracellular oxidation. This oxidative process is Fe2-,-dependent and is accompanied by an increase in intracellular calcium (35 nM). Both the intracellular oxidation and calcium rise induced by internalized bleomycin are inhibited by pretreatment of cells with varying concentrations of taurine (25, 125, and 187.5 uM). The inhibitory effect on intracellular oxidation .vas found to be 36, 57, and 60%, respectively. These results demonstrate a stimulation-inhibition relationship between bleomycin and taurine on re cellular oxidation at a subcytotoxic dose of bleomycin, suggesting that the oxidative effect of the intracellular bleomycin-Fe2 complex is important in the initiation of the fibrotic process. — Environ Health Perspect 102 (Suppl10):91-96 (1994) IntroductionThe pulmonary system is most susceptible to oxygen radical-induced diseases due to its constant exposure to the highest oxygen tension, and the potential encounters with oxidant gases such as ozone, nitrogen oxides, and toxic doses of dust particles. The lung is also a well-perfused organ and thereby vulnerable to the effect of circulating xenobiotics such as paraquat, and, bleomycin, which is known to cause pulmonary injuries (1). Alveolar macrophages (AM), which act as a means of defense by phagocytizing inhaled dust particles and microorganisms while increasing production of reactive oxidative species, have been shown to play an important role in mechanisms leading to oxidative lung injury and fibrosis (2-4)."

Dec 1, 1995

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Two other minerals, cryolite and fluorapatite, have significant fluorine content. Cryolite, sodium aluminum fluoride, Na3AlF,, is a rare mineral that has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. Fluorapatite, Ca5F(PO3)2, is a source of phosphate for fertilizer manufacture, containing a small percentage of fluorine. Commercially mined deposits of apatite have varying amounts of fluorine, chlorine, hydroxyl, and carbonate. HISTORY Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in 16th century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and 11. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s and the application of heavy media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological advances that facilitated increased production. Pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. USES OF FLUORITE Fluorspar is used to make hydrogen fluoride (HF), also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride is produced by reacting acid grade (97% CaF,) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation; the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, an ingredient in high-octane fuel for aircraft and automobiles; in steel pickling, enamel stripping, and glass etching and polishing; and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 12 to 29 kg of fluorine content in synthetic cryolite and aluminum fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly in countries with the most advanced technology (i.e., Australia and Sweden), while others (i.e., Surinam and South Africa), remain at the high end. Elemental fluorine is prepared from anhydrous hydrofluoric acid by electrolysis. Gaseous at room temperature and pressure, fluorine is compressed to a liquid for shipment in cylinders or in tank trucks. Elemental fluorine is used to make uranium hexafluoride, sulfur hexafluoride, and halogen fluorides. Gaseous uranium hexafluoride is used in separating U235 from U233 by the diffusion process. Sulfur hexafluoride is a stable high dielectric gas used in coaxial cables, transformers, and radar wave guides. Halogen fluorides have important applications, mostly as substitutes for elemental fluorine, which is more difficult to handle. Emulsified perfluorochemicals, organic compounds in which all hydrogen atoms have been replaced by fluorine, are undergoing investigation as promising blood substitutes. They transport oxygen and, in conjunction with a simulated blood serum, perform many functions of whole blood. With further development, these organic compounds may ultimately, in emergencies, be useful in saving lives of animals and humans during periods of acute shortages of natural blood. Inorganic fluorides are used as insecticides, preservatives, antiseptics, ceramic additives, and fluxes and in electroplating solutions, antioxidants, and many other products. Boron trifluoride is an important catalyst. Organic fluorides are volume leaders in the fluorine chemical industry. Fluorinated chlorocarbons and fluorocarbons are prepared by the interaction of anhydrous HF with chloroform, perchlorethylene and carbon tetrachloride, and are characterized by low toxicity and notable chemical stability. They perform outstandingly as refrigerants, aerosol propellants, solvents, and cleaning agents and as intermediates for polymers such as fluorocarbon resins and elastomers. Fluorocarbon resins are inert compounds that have unusually low coefficients of friction and have found a number of applications as lubricants for parts that cannot be oiled, e.g., bearings for window raising equipment located inside of automobile doors, in small electronic equipment, for the manufacture of chem-

Jan 1, 1994

By C. M. Bartley

Fluorspar, in addition to its familiar uses as a metallurgical flux and as a source of the electrolyte for aluminum production, has become important as an essential raw material in the rapidly growing fluorine chemical industry. The unique ability of fluorine to react and form compounds with al-most all other chemicals has made it one of the important elements in modern chemistry. Research and development over the past thirty years have resulted in a current annual production of fluorine chemicals that is both technically and economically important to industry. Because many of these chemicals and products are relatively new, and most have properties that are not duplicated by other materials, the present uses are expanding rapidly and new applications are being reported continually. Fluorspar, the only immediate and practical source of fluorine, is therefore an important mineral. This fact has been recognized in major industrial areas such as the United States and Western Europe, but has received little attention in Canada.

Jan 1, 1962

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By Henry T. Mudd

FLUORSPAR is a nonmetallic mineral aggregate or mass containing a sufficient quantity of fluorite (CaF2) to be of commercial interest. It has only moderate value per unit of weight and its cost as a percentage of the cost of finished consumer products is nearly negligible. Nevertheless, it has wide and great industrial importance. In periods of national emergency it is a mineral without which many very necessary manufacturing processes would be greatly handicapped; a few could not exist. Fluorite contains 51.1 pct calcium and 48.9 pct fluorine. Industrial grades of fluorspar prepared for the consumer normally contain from 85 to 98 pct fluorite, depending on the use. The ores may contain as little as 30 pct fluorite, depending on many factors such as accessibility to transportation and markets, character of ore, and prices. Fluorite is a lustrous, glasslike mineral, generally translucent to transparent; it may be clear and colorless or range in color from slightly bluish through various shades of violet, amethyst, purple, green, and yellow. It crystallizes in the isometric system and possesses perfect octahedral cleavage. Commonly it occurs in masses of very pure crystal- line material with aggregates of cubical crystals in open spaces, but - it is also found in fine to coarse granular form. Banded veins and masses with fibrous, radiating structure occur locally. It is usually found associated more or less intimately with other minerals and rocks, from which it must be separated for commercial use. The specific gravity of fluorite is 3.18 and the hardness is 4 in the Mohs scale, compared with 7 for quartz and 3 for calcite. It is distinguished from calcite by its failure to effervesce with dilute hydrochloric acid. Heated with sulphuric acid, it gives off fumes of hydro- fluoric acid, which etch glass.22,25,33.34,35.41

Jan 1, 1949

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By E. L. BROKENSHIRE

FLUORSPAR, a little known non-metallic mineral, referred to technically as fluorite, chemically as calcium fluoride, is a compound of calcium and fluorine in the ratio of one molecule of calcium to two of fluorine. By weight it is composed of 51.3 per cent of calcium and 48.7 per cent of fluorine. Its specific gravity is 3.2. It is brittle, has a hardness of four and can be easily scratched with a knife. It weighs about 200 Ib. per cubic foot and has a melting point of 1650" F. The color of fluorspar ranges from pure white and opaque white, according to its purity, to various hues of yellow, green, pink, lavender, blue and brown, to bluish black. Although the lumps have color, when ground the fluorspar becomes pure white. The reason for this is because the mineral usually carries no fixed pigment, the color being produced by the re- fraction of light rays within the crystal structure and small quantities of organic matter which readily oxidizes. It crystallizes in the isometric system with perfect octahedral cleavages.

Jan 1, 1929

By J. L. Gillson

IN a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. GENERAL STATEMENT ON FLUORSPAR SITUATION Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in I901 for $5.81, in 1916 for $5.92. When the United States entered World War I, fluorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $I8.00 per ton. By 1935 the average price had fallen to $15.00, but in 194o with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, 'or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. [ ] Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be- again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1945

By Gill Montgomery

The problems of the domestic merchant fluorspar producers are more or less common with those of many other producers of metallic and non-metallic minerals. For more than ten years the American fluorspar producers have seen an ever lowering price in the market-place for the fluorspar product, while their labor and material costs-continue to mount steadily. This cost-price squeeze has forced out of business all but a few of the merchant producers, and only two captive producers continue to operate, and one of them has announced early curtailment. The prices of domestic fluorspar, of all grades, have declined because of the competition from cheaper foreign imports, principally from Mexico, Spain and Italy. Tariff protection on fluorspar, particularly on the highest or acid grade, has never been sufficient to cover the production cost differential between foreign and domestic fluorspars. Low ocean and barge freight rates have also contributed to the barring of the product of domestic mines from, the major consuming centers along the Gulf and East Coast. Because of the freight disadvantage, all but one or two fluorspar producers in the western states have had to suspend business. More than 80% of the domestic fluorspar is being produced in Illinois and Kentucky fluorspar districts which adjoin on both sides of the Ohio River.

Jan 1, 1964

By R. M. Foley, Hidesaburo Kurushima

About 25 pct of all Japanese pyrite comes from the Yanahara mine on Honchu Island. For the past 40 years lack of an economical recovery process forced the operator, Dowa Mining Co., to sell the pyrite for its contained sulfur only, leaving 7 million tons of high grade iron ore waste. Introduction of the Dorrco FluoSolids roasting system enabled the company to make use of its iron sulfides and also to find a market for the mine's considerable pyrrhotite production. The success of this project is of great importance to Japan's economy since it points the way toward material increase in her natural resources. Prior to use of the present process, no practical method was available for commercial exploitation of known large tonnages of pyrrhotite, while the copper content of the even larger deposits of pyrite made the roasted residue unacceptable for the iron and steel industry. In Europe, large amounts of copper-bearing pyrite cinder are given a chloridizing roast for separation of the copper and iron but this treatment is not economical in Japan where salt is imported from as far away as Egypt.

Jan 10, 1958

By Animesh Jha, Chris Dometakis

"Without the use of a flux, only a poor dispersion of ceramic phase can be achieved. A molten-flux-assisted ceramic phase dispersion technique for producing aluminium alloy metalmatrix composites has been developed. In this paper, we report the physical chemistry for the dispersion of TiB2 in molten aluminium. In particular, aspects of the interfacial energy and the thermodynamics of the dispersion reactions are briefly discussed for enhancing the volume of dispersion phase in the molten metal and for controlling their morphology. This investigation also addresses the role of molten flux in the fabrication of AI-alloy mmc using a casting technique. The morphological aspects of the dispersion are explained on the basis of the classical theory· of nucleation.IntroductionMetal matrix composites (MMCs), have long been recognised as an important class of material due to their greater wear resistance, specific stiffness and temperature capability when compared to conventional monolithic alloys. Particulate reinforced composites produced by melt casting techniques have been amongst the first MMCs to achieve commercial market viability. The advent of melt mixing techniques such as the Duralcan™ process have enabled low cost, easily fabricated composites based on the AI-SiC and AIAlz0 3 systems to be produced. In this process, uncoated ceramic particles with diameters 10ltm and larger, are incorporated into conventional monolithic alloys with reinforcement levels up to 25 volume percent. The AI-7Si-SiC metal-matrix composites have good wear resistance, high strength, low density and high thermal conductivity. The combination of these physical and mechanical properties has become a major attraction for the fabrication of light-alloy composite disc rotor brakes for the automotive sector2. However, in silicon-free alloys, SiC is thermodynamically unstable above the composite melting point and is extensively attacked by the melt to form aluminium carbide3 :"

Jan 1, 1996

By Ernest B. Snyder

The word "line" has been used loosely for many forms of the common steel plant flux. For example, many people use the word "lime" for nigh calcium and dolomitic limestone, for high calcium and dolomitic quicklime (also called caustic lime, calcined lime; burnt lime, pulverized and pebble lime) and ;van for clinkered dolomite. Calcium hydroxide, also called slaked lime and hydrated lime, is called "lime" but is seldom used as a flux except when the quicklime air slakes in open boxes or bins. All of the above forms of "lime" are used in the steel plant. Calcium hydroxide is used for water treatment, acid neutralizing, and as a lubricant for wire drawing. All the other limes are used as fluxes in the sintering plant, blast furnace or steel producing furnaces. In the production of self-flux or super-flux sinter, high calcium and dolomitic limestone fines are used. Where quicklime fines are available, they may be added to the sinter mix also. The blast furnace uses both high calcium and/or dolomitic limestone. A few trials have been made using iron oxide stabilized dolomitic lime in an attempt to reduce coke consumption and to increase the production rate. The trials were very successful but would' not be economical, except in periods of coke shortages, with resulting extremely high coke cost and exceptionally high hot metal demand.

Jan 1, 1979

By P Kumar, J Safarian

Understanding how ore interacts with flux particles at elevated temperatures to create molten slag is crucial since it governs the dynamics of a chemical reaction. This study explores the smelting behaviour of pre-reduced Nchwaning manganese ore when combined with lime, with the objective of examining the evolving interaction between pre-reduced ore particles and lime over time. The research sheds light on the interaction between solid and liquid and the phases that emerge during this process. To achieve this, a sessile drop furnace was employed to rapidly heat the materials positioned adjacent to each other on an alumina substrate and to observe the smelting process as it unfolded over time. This method allowed for the direct observation of the melting temperatures and the flux-ore reaction progression rate, and the potential disruptive events that might occur. By comparing the molten interfaces of the fluxed materials at various time intervals, this study provides insights into the relative rate of slag formation from the two materials. The results indicate that the main slag formation initiated at approximately 1400°C and continued to advance with time, with complete mixing occurring around 1500°C. The possible phases formed were identified using Scanning Electron Microscopy and modelled using Fact Sage thermodynamic software. In addition, the iron particles in the pre-reduced Mn ore were separated and settled from a rich MnO-containing slag. It was found that the separation of molten iron droplets from the slag depends on the rate of solid MnO particles dissolution into the adjacent slag phase.

Jun 19, 2024

By K Vallo, T Haimi, J Pihlasalo, J Hamuyuni, M Lindgren, F Tesfaye

Decarbonisation of the steel industry has recently attracted a lot of research and technological development. Most of the technological developments are centred around the replacement of blast furnace (BF), which has been the main primary smelting furnace in the ironmaking step of steel production. Replacement of the BF is not an easy task because of BF’s many established capabilities over the years, especially its ability to use low-grade iron feed. In this regard, Metso has developed its own technology, Metso’s Outotec direct reduced iron (DRI) smelting furnace, to tackle this problem. The recently developed six-in line electric furnace for DRI smelting can be used for primary smelting of DRI from blast furnace grade iron ore. Unlike the electric arc furnace (EAF), the DRI smelting furnace can handle larger slag volumes that emanate from the high gangue in BF grade DRI. Therefore, fluxing plays an important role in operating the DRI smelting furnace. This paper presents fluxing options and proposes slag quality and operating windows for the DRI smelting furnace. Also, the effect of slag on refractory durability will be discussed.

Jun 19, 2024

By J. G. Groppo

In 1992, 48 million tons of fly ash (not including bottom ash, boiler slag and FGD material) was produced in the United States, according to the American Coal Ash Association. Of this amount, 27.2% was utilized; although the percentage of fly ash utilized increased from 20% in 1980, there is significant potential to increase utilization. One of the primary driving forces behind increased utilization is increased disposal costs due to more stringent environmental controls and regulation. Fly ash is classified as a natural pozzolan and finds significant use as a cement additive. It has been found to increase the plasticity of the cement mixture while lowering the amount of mix water needed. In addition to improving leveling and finishing properties, fly ash improves pumpability as well as decreases the heat of hydration of the concrete mix which is particularly important in massive concrete structures such as dams where the concrete needs to cool as quickly as possible. The Loss on Ignition (LOI) of fly ash is an important quality when considering utilization. The LOI is primarily due to the presence of unburned carbon and the standard specifications for the use of fly ash as a mineral admixture in Portland cement concrete are given in ASTM C618-89a. which sets an LOI limit of 6%. However, many states have set a more stringent limit of 3%. The primary reason for the lower LOI specification is that carbon adsorbs air entraining agents which limits freeze-thaw resistance. This is particularly important in climates such as the midwestern US where multiple cycles of freezing and thawing are typical in winter.

Jan 1, 1995