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Rare earth (RE) doped oxyfluoride glass ceramics possess interesting optical properties with applications in telecommunications and optoelectronics, such as solid state lasers, optical amplifiers, etc. These materials combine the transparency and mechanical and chemical resistance of aluminosilicate glasses with the low phonon energy and facile incorporation of RE ions in the fluoride crystals. The incorporation of RE ions in the crystalline phases enhances the laser emission intensity, a major property of these materials. Transparency is achieved when crystal size is in the nanometric scale, usually below 40 nm, which avoids light scattering. A strict control of the nucleation and crystal growth processes is therefore necessary which requires a deep knowledge of the crystallisation mechanisms. The great activity and publications in this field in the last decades merit a review providing a comparative study of the different nanoglass ceramic systems, their structural and optical characterisation and their main properties and applications. This is the objective of this review paper which includes 232 references. A general discussion on glass nucleation and crystallisation theories and more relevant crystallisation parameters and characterisation techniques are put forward in the first section of the review, focused on nanocrystallisation processes in oxyfluoride systems. In the second section, the principal RE doped glass ceramics are presented. After a general introduction about the luminescence processes, including up-and down-conversion, the behaviour of RE elements in glasses and crystals are discussed. Glass ceramic compositions have been divided as follows: glass ceramics with a glass composition following Wang and Ohwaki's oxyfluoride glass ceramic, 1 ; and glass ceramics with different matrix compositions, arranged by crystalline phases. Relevant properties, mainly optical and laser, are described in each system along with the most relevant applications of these materials.

Nanocrystallization of LaF 3 in a glass of composition 55SiO 2 -20Al 2 O 3 -15Na 2 O-10LaF 3 (mol%) has been achieved by heat treatment above the glass transition temperature. A maximum crystal size of 14 nm has been attained, with the crystalline fraction and crystal size dependent on the time and temperature of thermal treatment. The effect of lanthanum fluoride crystallization is noticeable from the microstructural and compositional changes in the glass matrix, which have been studied using several techniques, including viscosity, dilatometry, X-ray diffraction, and quantitative Rietveld refinement, transmission electron microscopy, and differential scanning calorimetry. The crystallization mechanism is shown to occur via regions of La-and Si-phase separation in the glass, from which the fluoride crystals develop during heat treatment. The interface between the glass matrix and the crystals in the demixed ranges is enriched in network formers, mainly SiO 2 , creating a viscous barrier, which inhibits further crystal growth and limits the crystal size to the nanometric range.

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Yttrium silicate (Y 2 SiO 5 ) coatings complement SiC coatings for protecting ceramic multilayer composite materials based on carbon-fiber-reinforced SiC composites (C-SiC). Thick (100 m), dense Y 2 SiO 5 coatings were prepared by dip coating, using concentrated aqueous slips. The resulting phases were studied by taking into account the simultaneous presence of oxide and non-oxide materials, which affected the chemical stability of the coatings. Thick, mechanically stable coatings were obtained by sintering in carbon crucibles and a SiC bed in an argon-flow furnace. Pure Y 2 SiO 5 coatings completely separated from the SiC substrates. A high percentage of Y 2 Si 2 O 7 was necessary to fit the thermal expansion coefficients and ensure the stability of the coatings. Oxidation resistance of the coated substrates was investigated by isothermal and stepwise oxidation tests.