Elemental fluorine (F) is not readily available in nature, instead, in the form of fluorine minerals such as fluorite (CaF2), fluropatite (3Ca3(PO4)2.Ca(ClF)), and cryolite (Na3AlF6). Some of the other fluorine minerals include artroeite, creedite, fluocerite, frankdicksonite, rosenbergite, and sellaite. Fluorine is the 13th most common element in the Earth’s crust. Free-form fluorine is a pale yellow gas with diatomic structure (F2) and of a corrosive, very toxic, and oxidizing nature. Elemental fluorine gas can also ignite some organic materials.
The key reason for unavailability of elemental fluorine is its extreme reactivity. It is the most reactive halogen and one of the most reactive elements in the periodic table. Moreover, fluorine can react with noble gases to form stable compounds such as xenon difluoride, tetrafluoride, hexafluoride, and oxytetrafluoride. Neon fluorides do exist; however, they are short-lived. Additionally, elemental fluorine can form compounds with krypton, radon, argon, and helium.
Fluorine has 18 known isotopes, ranging from F-14 to F-31; however, only one of them is stable (F-19), containing 10 neutrons. The radioactive isotope 18F is a valuable source of positrons. Large-scale production of elemental fluorine began during World War II. The expanding nuclear industry is a key reason for the development of the fluorochemical industry in the post-war era. In terms of application, the market for elemental fluorine can be segmented into plasma etching, flat panel display production, microelectromechanical systems (MEMS), and organic syntheses reactions.
Fluorine and fluorine-containing gases have applications in plasma etching as insulators with high electric fields (such as around linear accelerators). The electronegativity of these gases is the determining factor of the DC voltage, when all other process parameters remain constant. These gases decrease the density of the free electrons in the plasma, which increases the number of negative ions.
Fluorine gas is a substitute for gases (such as nitrogen trifluoride (NF3) and sulfur hexafluoride (SF6)) with a high global warming potential. It is employed in cleaning chemical vapor deposition (CVD) chambers in the manufacture of flat panel displays. Xenon difluoride (XeF2) is employed as dry vapor phase isotropic etch for releasing metal and dielectric structures in microelectromechanical systems (MEMS) fabrication. XeF2 has the advantage of a stiction-free release, unlike wet etchants. Elemental fluorine is also used in various organic synthesis reactions such as production of commercially unavailable fluorinating reagents, electrophilic aromatic substitution, nitrogen derivatives, and fluorination of double bonds.
Usage of elemental fluorine in fluorination of double bonds is now preferred over the method of reacting olefins with Pb(OAc)4 and HF. Simple and efficient production of acetyl hypofluorite can be carried out with the help of fluorine (F2) gas and sodium acetate. Elemental fluorine is employed for fluorination of activated aromatic compounds, synthesizing biologically important fluorine containing derivatives, and in positron emitting tomography (PET). Under restrained situations, high reactivity of elemental fluorine can break almost any organic compound or perfluorinate it. However, under the right set of conditions, it may act as a powerful electrophile instead.
China and Mexico are prominent producers of fluorine and its compounds. These countries hold large reserves, along with South Africa and Mongolia. In terms of consumption of elemental fluorine, Asia Pacific is likely to dominate the global market, particularly countries such as China, Japan, and South Korea. North America and Europe are likely to exhibit similar demand, with the former leading among the two regions. A similar trend is expected to be observed with Latin America and Middle East & Africa, with Latin America leading the demand for elemental fluorine between the two regions.
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Key players operating in the elemental fluorine market include Solvay, The Linde Group, Air Products and Chemicals Inc., and Pelchem SOC Ltd.