Design, processing and characterization of glass fibers and coatings for healthcare industries

In this PhD, several bioactive phosphate glasses doped with erbium ions (Er3+) were synthesized and characterized in order to develop new bioactive fiber sensors for medical diagnostics and therapeutics in healthcare applications. Firstly, Er3+-doped phosphate glasses within the glass system P2O5-SrO-Na2O were fabricated using the melt-quenching technique. The glasses were prepared with different compositions and analyzed to understand the impact of the addition of Al2O3, TiO2 or ZnO on the thermal, structural and luminescence properties of the glasses. The results showed that with the addition of Al2O3 and TiO2 the phosphate network became more connected, whereas the addition of ZnO did not modify the optical, thermal and structural properties but it led to an enhanced fluorescence emission as compared to the other glasses. Secondly, glass-ceramics (GCs) were processed by heat-treating the glasses to induce in-situ crystal growth. The effect of the crystallization on the properties of phosphate glasses containing Al2O3, TiO2 or ZnO was investigated. The structural, optical, and spectroscopic characterization allowed assessing the occurrence and properties of the Er3+-doped crystals in the glasses. Different crystal phases were obtained depending on the glass composition but Sr(PO3)2 was identified in all the glasses. Moreover, the surface crystallization of the GCs was increased along with the duration of the heat treatment. However, the site of the Er3+ ions was not strongly affected by the heat treatment except for the reference GC, where an increase of the luminescence properties was observed after the heat treatment probably due to the incorporation of Er3+ ions into the crystals. Thirdly, particles-containing glasses were prepared using the direct doping method. A series of different Er3+-doped Al2O3, TiO2, ZnO and ZrO2 nano- and microparticles were synthesized using soft chemistry and then were added to phosphate-based glass batches prior to and after the melting. The survival and dispersion of the particles were optimized in order to increase the luminescence properties of the glasses. As evidenced by the morphological and compositional analyses, the Er3+ ions diffused from the particles to the glass matrix and no improvement of the spectroscopic properties was observed. A large amount of Er3+-doped particles were dissolved into the glasses probably due to the high temperatures achieved during the melting. As an alternative, glasses with different composition and lower melting temperatures were tested. The last part of the project was the production and characterization of a multimode optical fiber made from phosphate-based glasses. The core composition was 0.25 Er2O3 – 97.25 (0.5 P2O5 – 0.4 SrO – 0.1 Na2O) – 2.5 ZnO, while the cladding composition was 98.25 (0.5 P2O5 – 0.4 SrO – 0.1 Na2O) – 1.75 ZnO. The cladding component was processed using the rotational casting technique, and the preform was successfully drawn into an optical fiber. This novel optical fiber was found to be able to allow in-line monitoring of the fiber dissolution in H3PO4 and in simulated body fluid (SBF) solution. Bioactivity of the fiber was also assessed by the formation of a hydroxylapatite layer at the surface of the fiber after 4 weeks of immersion in SBF solution at room temperature. In this thesis, a bioactive fiber sensor able to monitor its optical properties and in vitro reactivity was reported. This research activity demonstrates as a proof of principle the idea of tracking the bio-response of a bioactive optical fiber “in vivo”.