Fluoridation scale

Perimeter Polyacrylonitrile Poly-vinylidene fluoride Scaling ratio... 

FIGURE 2.6 SEM images of etched channels illustrating the dependence of the smoothness of the etched surface on the etching solution. (A) SEM image of the channel etched with a high concentration of buffered HF (32% HF buffered with a 1 1 ratio of HF to ammonium fluoride) (scale bar 150 pm). (B) SEM image of the channel etched with a low concentration of non-buffered HF solution (10% HF) (scale bar 100 pm) [125], Reprinted with permission from Elsevier Science. 

Calcium fluoride scale can form when the concentration of fluoride is as low as 0.1 ppm if the concentration of calcium is high. Scaling will occur when the ion product exceeds the solubility constant. Antisealants or sodium softening can be used to control calcium fluoride scale. 

Antisealants are usually fed alone for most applications. Acid feed is sometime used in conjunction with an antisealant to control LSI for calcium carbonate scale and to control calcium phosphate and calcium fluoride scales. Antisealants currently on the market are not generally effective at controlling calcium phosphate scale and have difficulty controlling calcium carbonate scale when the LSI is greater than about +2, depending... 

Acid feed acid is added to reduce the LSI and calcium carbonate, calcium phosphate or calcuim fluoride scaling potential, if required. 

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

Hydrogen fluoride is the most important compound of fluorine. It is prepared in the laboratory, and on the large scale, by the reaction of calcium fluoride with concentrated sulphuric acid. ... 

Disposal. Fluorine can be disposed of by conversion to gaseous perfluorocarbons or fluoride salts. Because of the long atmospheric lifetimes of gaseous perfluorocarbons (see Atmospheric models), disposal by conversion to fluoride salts is preferred. The following methods are recommended scmbbing with caustic solutions (115,116) reaction with soHd disposal agents such as alumina, limestone, lime, and soda lime (117,118) and reaction with superheated steam (119). Scmbbing with caustic solution and, for dilute streams, reaction with limestone, are practiced on an industrial scale. 

Molybdenum hexafluoride is used in the manufacture of thin films (qv) for large-scale integrated circuits (qv) commonly known as LSIC systems (3,4), in the manufacture of metallised ceramics (see MetaL-MATRIX COMPOSITES) (5), and chemical vapor deposition of molybdenum and molybdenum—tungsten alloys (see Molybdenumand molybdenum alloys) (6,7). The latter process involves the reduction of gaseous metal fluorides by hydrogen at elevated temperatures to produce metals or their alloys such as molybdenum—tungsten, molybdenum—tungsten—rhenium, or molybdenum—rhenium alloys. 

Manufacture and Economics. Nitrogen tritiuoride can be formed from a wide variety of chemical reactions. Only two processes have been technically and economically feasible for large-scale production the electrolysis of molten ammonium acid fluoride and the direct fluorination of the ammonia in the presence of molten ammonium fluoride. In the electrolytic process, NF is produced at the anode and H2 is produced at the cathode. In a divided cell of 4 kA having nickel anodes, extensive dilution of the gas streams with N2 was used to prevent explosive reactions between NF and H2 (17). 

Silver difluoride, commercially available from the same sources as those of AgF, had a 1993 price between 1000— 1400/kg. In spite of the technical success in laboratory experiments, silver fluorides have found limited use on a large scale mainly because of the high cost of the reagents. Demand for silver difluoride is less than 100 kg/yr. 

ECF is successfully used on a commercial scale to produce certain perfluoroacyl fluorides, perfluoroalkylsulfonyl fluorides, perfluoroalkyl ethers, and perfluoroalkylamines. The perfluoroacyl fluorides and perfluoroalkylsulfonyl fluorides can be hydrolyzed to form the corresponding acid and acid derivatives. Examples include perfluorooctanoyl fluoride [335-66-0] perfluorooctanoic acid [335-67-1] perfluorooctanesulfonyl fluoride [307-35-7] perfluorooctanesulfonic acid [763-23-1] and tris(perfluoro- -butyl)amine [311-89-7]. 

Aromatic Ring Fluorination. The formation of an aryl diazonium fluoride salt, followed by decomposition, is a classical reaction (the Schiemaim reaction) for aryl fluoride preparation (21). This method has been adapted to the production-scale manufacture of fluorobenzene [462-06-6]... 

Fluoroaromatics are produced on an industrial scale by diazotization of substituted anilines with sodium nitrite or other nitrosating agents in anhydrous hydrogen fluoride, followed by in situ decomposition (fluorodediazoniation) of the aryldiazonium fluoride (21). The decomposition temperature depends on the stabiHty of the diazonium fluoride (22,23). A significant development was the addition of pyridine (24), tertiary amines (25), and ammonium fluoride (or bifluoride) (26,27) to permit higher decomposition temperatures (>50° C) under atmospheric pressure with minimum hydrogen fluoride loss. 

This represents the first large-scale appHcation of a fluoroaryl organometaOic. Other silicon-containing aryl fluorides such as pentafluorophenyldimethyl silanes, CgF Si(CH2)2X (X = Cl NH2 N(0211 )2), are offered commercially as Flophemsyl reagents for derivati2ation of sterols in chromatographic analysis (166). 

A small by-product stream is also realized in Europe from glass-etching by HF. Laboratory-scale production is readily accomphshed by exchange between metal fluorides and chlorosilanes (172). 

A hydrochloric acid process for the manufacture of anatase has been proposed but has not been developed. Other routes include fluoride, bromide, nitrate, sulfide, and chloroacetate processes (1). None of these, however, has been used successfully on a commercial scale. 

In the late 1950s, the copolymers of vinyUdene fluoride and hexafluoropropylene, CF2=CFCF3, were developed on a commercial scale by 3M (Fluorel) and by Du Pont (Viton) (5—8). In the 1960s, terpolymers of vinyUdene fluoride, hexafluoropropylene, and tetrafluoroethylene, CF2=CF2, were developed (9) and were commercialized by Du Pont as Viton B. At about the same time, Montedison developed copolymers of vinyUdene fluoride and 1-hydropentafluoropropylene as well as terpolymers of these monomers with tetrafluoroethylene, marketed as Tecnoflon polymers (10,11). 

The hardness of a mineral as measured by the Mohs scale is a criterion of its resistance to crushing [Fahrenwald, Trans. Am. In.st. Min. Metall. Pet. Eng., 112, 88 (1934)]. It is a fairly good indication of the abrasive character of the mineral, a factor that determines the wear on the grinding media. Arranged in increasing order or hardness, the Mohs scale is as fohows 1, talc 2, gypsum 3, calcite 4, fluoride 5, apatite 6, feldspar 7, quartz 8, topaz 9, corundum and 10, diamond. 

A number of attempts to produce tire refractory metals, such as titanium and zirconium, by molten chloride electrolysis have not met widr success with two exceptions. The electrolysis of caesium salts such as Cs2ZrCl6 and CsTaCle, and of the fluorides Na2ZrF6 and NaTaFg have produced satisfactoty products on the laboratory scale (Flengas and Pint, 1969) but other systems have produced merely metallic dusts aird dendritic deposits. These observations suggest tlrat, as in tire case of metal deposition from aqueous electrolytes, e.g. Ag from Ag(CN)/ instead of from AgNOj, tire formation of stable metal complexes in tire liquid electrolyte is the key to success. 

The harmful effects of air pollutants on human beings have been the major reason for efforts to understand and control their sources. During the past two decades, research on acidic deposition on water-based ecosystems has helped to reemphasize the importance of air pollutants in other receptors, such as soil-based ecosystems (1). When discussing the impact of air pollutants on ecosystems, the matter of scale becomes important. We will discuss three examples of elements which interact with air, water, and soil media on different geographic scales. These are the carbon cycle on a global scale, the sulfur cycle on a regional scale, and the fluoride cycle on a local scale. 

The movement of fluoride through the atmosphere and into a food chain illustrates an air-water interaction at the local scale (<100 km) (3). Industrial sources of fluoride include phosphate fertilizer, aluminum, and glass manufacturing plants. Domestic livestock in the vicinity of substantial fluoride sources are exposed to fluoride by ingestion of forage crops. Fluoride released into the air by industry is deposited and accumulated in vegetation. Its concentration is sufficient to cause damage to the teeth and bone structure of the animals that consume the crops. 

In addition to the elastomers already described, others, have been produced on an experimental scale. These include the perfluoroalkylenetriazines with their unsurpassed thermal oxidative stability for an elastomer but with many offsetting disadvantages, and polyfthiocarbonyl fluoride). It is probably true to say that material does not have any outstanding desirable property that cannot now be matched by an alternative and commercially available material. 

Xenon difluoride [4, 5, 7, 8,10] is a white crystalline material obtained through the combination of fluorine and xenon m the presence of light The reagent is commercially available and possesses a relatively long shelf-life when stored cold (freezer) Xenon difluoride is very effective for small-scale fluormation of alkenes and activated nucleophilic substrates. The reactions are usually conducted between 0 °C and room temperature in chloroform or methylene chloride solutions Hydrogen fluoride catalysis is sometimes helpful Xenon difluoride reacts in a manner that usually involves some complexation between the substrate and reagent followed by the formation of radical and radical cation intermediates... 

Fluoroaromatics are now produced m 75-90% yields on an industrial scale by this method The nonorganic layer containing water, hydrogen fluoride, and sodium bifluoride is treated with sulfur trioxide, and anhydrous hydrogen fluoride is recycled by distillation [54 (equation 13)... 

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