Fluorapatite

The hexafluorosilicic acid solutions produced as a byproduct in the production of phosphoric acid by the digestion of apatite [Ca (P04)2 Cap2 with 2-4% fluorine content, byproduct silicon dioxide] with sulfuric acid are important raw materials for the manufacture of fluorochemicals (e.g. manufacture of sodium fluoride NaF). The reserves of available fluorine from fluorapatite are estimated to be 327 10 t Cap2 (of which 32 10 t is in the USA), the fluorine quantities available in fluorapatite being therefore considerably greater than the fluorspar reserves. However, the industrial exploitation is still negligible. The reasons therefor are that  

Nevertheless, it is expected that this source of fluorine will become more important in the future. 

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The ores of most importance are fluorspar, CaF2 fluorapatite, Ca (P0 2Fj cryoHte [15096-52-3], Na AlF. Fluorspar is the primary commercial source of fluoiine. Twenty-six percent of the world s high quaHty deposits of fluorspar are ia North America. Most of that is ia Mexico. United States production ia 1987—1991 was 314,500 metric tons, most of which occurred ia the Illinois-Kentucky area. Imported fluorspar ia 1990—1991 represented about 82% of U.S. consumption 31% of U.S. fluorspar imports were from Mexico and 29% from China compared to 66% from Mexico ia the 1973—1978 period. The majority of the fluorine ia the earth s cmst is ia phosphate rock ia the form of fluorapatite which has an average fluorine concentration of 3.5%. Recovery of these fluorine values as by-product fluorosiHcic acid from phosphate production has grown steadily, partially because of environmental requirements (see Phosphoric acid and THE phosphates). 

Phospha.tes. Many phosphates cl aim unique material advantages over siUcates that make them worth the higher material costs for certain apphcations. Glass-ceramics containing the calcium orthophosphate apatite, for example, have demonstrated good biocompatibiUty and, in some cases even bioactivity (the abiUty to bond with bone) (25). Recent combinations of fluorapatite with phlogopite mica provide bioactivity as well as machinability and show promise as surgical implants (26). 

Phosphorus [7723-14-0] is a nonmetaUic element having widespread occurrence in nature as phosphate compounds (see Phosphoric acid and phosphates). Fluorapatite [1306-03-4], Ca F(P0 2> is the primary mineral in phosphate rock ores from which useful phosphoms compounds (qv) ate produced. The recovery from the ore into commercial chemicals is accompHshed by two routes the electric furnace process, which yields elemental phosphoms and the wet acid process, which generates phosphoric acid. The former is discussed herein (see Furnaces, electric). Less than 10% of the phosphate rock mined in the world is processed in electric furnaces. Over 90% is processed by the wet process, used primarily to make fertilisers (qv). 

Elemental phosphoms is produced from a phosphoms-rich ore mostiy recovered by strip mining. This ore usually contains fluorapatite, plus some sihca and siUcates. When a carbon source, usually coke, is added to the ore at temperatures greater than 1100°C, the following overall reaction occurs ... 

Phosphates. The primary constituent of phosphate rock is fluorapatite, Ca3FP2022- Industrial phosphates including phosphate fertilizers (qv), phosphoric acid, and calcium phosphates (11) (see Phosphoric acid and the phosphates) are obtained from the large deposits of fluorapatite found in Florida in the United States, and in Morocco. Because phosphate rock is too insoluble to be useful as a fertilizer, it is converted to superphosphate [12431 -88-8] Ca(H2P0 2 CaSO, by H2SO and to triple superphosphate [7758-23-8] by H PO (l )- Phosphoric acid may also be... 

Phosphorus is the eleventh element in order of abundance in crustal rocks of the earth and it occurs there to the extent of 1120 ppm (cf. H 1520 ppm, Mn 1060 ppm). All its known terrestrial minerals are orthophosphates though the reduced phosphide mineral schrieber-site (Fe,Ni)3P occurs in most iron meteorites. Some 200 crystalline phosphate minerals have been described, but by far the major amount of P occurs in a single mineral family, the apatites, and these are the only ones of industrial importance, the others being rare curiosities. Apatites (p. 523) have the idealized general formula 3Ca3(P04)2.CaX2, that is Caio(P04)6X2, and common members are fluorapatite Ca5(P04)3p, chloroapatite Ca5(P04)3Cl, and hydroxyapatite Ca5(P04)3(0H). In addition, there are vast deposits of amorphous phosphate rock, phosphorite, which approximates in composition to fluoroapatite. " These deposits are widely... 

The principal agents of tooth decay are the carboxylic acids produced when bacteria act on the remains of food. A more resistant coating forms when the OH ions in the apatite are replaced by F ions. The resulting mineral is called fluorapatite ... 

Fluorine comes from the minerals fluorspar, CaF, cryolite, Na3AlF6 and the fluorapatites, Ca,F(P04)3. The free element is prepared from HF and KF by electrolysis, but the HF and KF needed for the electrolysis are prepared in the laboratory. Chlorine primarily comes from the mineral rock salt, NaCl. The pure element is obtained by electrolysis of liquid NaCl. Bromine is found in seawater and brine wells as the Br ion it ts also found as a component of saline deposits the pure element is obtained by oxidation of Br (aq) by Cl,(g). Iodine is found in seawater, seaweed, and brine wells as the I" ion the pure element is obtained by oxidation of I (aq) by Cl,(g). 

By far the most abundant phosphate mineral is apatite, which accounts for more than 95% of all P in the Earth s crust. The basic composition of apatite is listed in Table 14-2. Apatite exhibits a hexagonal crystal structure with long open channels parallel to the c-axis. In its pure form, F , OH , or Cl occupies sites along this axis to form fluorapatite, hydroxyapatite, or chlor-apatite, respectively. However, because of the "open" nature of the apatite crystal lattice, many minor substitutions are possible and "pure" forms of apatite as depicted by the general formula in Table 14-2 are rarely found. 

Of the possible substituting ions, COi ion is by far the most important followed by Na, S04 and Mg. The most common form of natural apatite in sedimentary rocks is francolite, a substituted form of carbonate fluorapatite deposited in marine systems. The substitution of col ior>s into the mineral lattice has a substantial effect on apatite solubility (Jahnke, 1984). More studies are required, however, before the effects of all substituting ions are imderstood and an accurate assessment of the solubility of complex, natural apatites can be made. 

Minerals can form colorful regular crystals. Shown here are vanadinite, Pbj (V04)3 Cl lefty, quartz, Si02 center)-, fluorapatite, Caj (P04)3 F top right)-, and stibnite,... 

Kniep R, Simon P (2007) Fluorapatite-Gelatine-Nanocomposites Self-Organized Morphogenesis, Real Structure and Relations to Natural Hard Materials. 270 73-125 Koenig BW (2007) Residual Dipolar Couplings Report on the Active Conformation of Rhodopsin-Bound Protein Fragments. 272 187-216 Kolusheva S, see Jelinek R (2007) 277 155-180... 

Once fluoride ions react with bone, they are not easily dissolved out or exchanged by other elements. If bone is buried for long periods of time, the relative amount of fluorine in the bone gradually increases as a function of time the "fluoridation" process continues until the maximum amount of fluorine (necessary to convert all the hydroxyapatite to fluorapatite) is reached. The total concentration of fluor in carbonated fluorapatite can reach levels as high as above 3%. There is ample room, therefore, for an increase in the relative amount of fluorine in buried bone. Determining the relative amount of fluorine in buried bone may thus serve as a tool for dating bone. 

Fig. 1.7 Scanning electron micrographs showing fractal pattern formation by hierarchical growth of fluorapatite-gelatin nanocomposites (A) half of a dumbbell aggregate viewed along the central seed axis, (B) dumbbell aggregate at an intermediate growth state, and (C) central seed exhibiting tendencies of splitting at both ends ( small dumbbell). Adapted from [119], reproduced by permission ofWiley-VCH.

Crystallization of the amorphous layer by incorporation of OH-, C032- or F- anions from solution to form a mixed hydroxyl carbonate fluorapatite layer (CHA). 

Figure 8.9 Sources of phosphorus (a) fluorapatite (b) the mineral schreibersite (c) alkyl phos-phonic acids...

Fluorapatite is the only significant phosphorus-containing mineral in the Earth s crust and schreibersite has been found in iron meteorites. The only organic species to be found containing phosphorus in meteorites are the alkyl phosphonic acids. These are at least promising even if they do not contain the P-O-P phosphoester bond unit. 

CCP in milk is mentioned in connection with casein above (Section VI.C). Fluorapatite is a major constituent of phosphate rocks, and a constituent, probably important, of human tooth enamel for those whose drinking water contains significant amounts of naturally occurring or added fluoride. Fluorapatite is significantly less soluble than hydroxyapatite - the relationship between the solubilities of fluorapatite and hydroxyapatite parallels (but is much less extreme than) that between calcium fluoride (Ksp — 3.9 x 10 11 mol3 dm-9) and calcium hydroxide (Ksp = 7.9 x 10 6 mol3 dm 9). Calcium diphosphate, Ca2P207, is believed to be the least soluble of the calcium phosphates. 

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