The development of low-loss fluoride glass fibres for transoceanic telecommunications led to an increased demand for inorganic fluorides with ultrahigh purity in respect of transition metals, rare earths and oxygen. This review paper describes the Merck Ltd strategy for achieving a wide range of metallic fluorides using methods of preparation and purification selected for a combination of technical efficacy and economic practicability. General preparative methods involving aqueous and non-aqueous routes are described, together with purification methods such as ion exchange, zone refining and vacuum sublimation. The special role of ammonium fluoride complexes is discussed. The application of these general methods to the manufacture of fluoride glass components is described, with special reference to the ZBLAN formulation. Additional glass compositions and their individual requirements are also discussed. The parallel application of high-purity metal fluorides in the growth of optical crystals is emphasised, the history of fluoride ultrapurification having begun with the early demand for high-quality UV and IR crystals such as CaF, and LiF.
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