Self-Healing Glassy Thin Coating for High-Temperature Applications.

Glass thin films (with nanometer to micrometer thicknesses) are promising in numerous applications, both as passive coatings and as active components. Self-healing is a feature of many current technological developments as a means of increasing the lifetime of materials. In the context of these developments, we report on the elaboration of the first self-healing glassy thin-film coating developed specifically for high-temperature applications. This coating is obtained by pulsed laser deposition of alternating layers of vanadium boride (VB) and a multicomponent oxide glass. Self-healing is obtained through the oxidation of VB at the operating temperature. The investigation of the effect of elaboration parameters on the coating composition and morphology made it possible to obtain up to seven-layer coatings, with good homogeneity and perfect interfaces, and with a total thickness of less than 1 µm. The autonomic self-healing capacity of the coating has been demonstrated by an in situ experiment, which shows that a crack of nanometric dimension can be healed within a few minutes at 700 °C.

Immobilization of radioactive iodine in silver aluminophosphate glasses.

Silver aluminophosphate glasses have been investigated as matrices for the immobilization of radioactive iodine. In this study, up to 28mol% AgI have been incorporated without volatilization thanks to a low temperature synthesis protocol. Alumina was added in the composition in order to increase the glass transition temperature for a better thermal stability in a repository conditions. Two series of glasses have been investigated, based on AgPO3 and Ag5P3O10 compositions, and with 0-5mol% Al2O3. We report (31)P, (27)Al and (109)Ag NMR study of these glasses, including advanced measurement of the connectivities through {(27)Al}-(31)P cross-polarization and (31)P-(31)P double-quantum correlation. We confirm that AgI is inserted in the aluminophosphate glasses and does not form clusters. AgI does not induce any modification of the glass polymerization but only an expansion of the network. Despite no evidence for crystallization could be obtained from XRD, NMR revealed that the introduction of AgI induces an exclusion of alumina from the network, leading to the crystallization of aluminophosphate phases such as Al(PO3)3 or AlPO4. As a consequence, despite NMR gives evidence for the presence of aluminophosphate bonds, only a limited effect of alumina addition on thermal properties is observed.

Characterization of lead, barium and strontium leachability from foam glasses elaborated using waste cathode ray-tube glasses.

Foam glass manufacture is a promising mode for re-using cathode ray tube (CRT) glasses. Nevertheless, because CRTs employ glasses containing heavy metals such as lead, barium and strontium, the leaching behaviour of foam glasses fabricated from CRTs must be understood. Using the AFNOR X 31-210 leaching assessment procedure, the degree of element inertization in foam glasses synthesized from waste CRT glasses (funnel and panel glasses, containing lead and barium/strontium respectively) were determined. The amount of leached lead from foam glasses prepared from funnel glass depends on the nature and concentration of the reducing agent. The effects of the reducing agents on the generation of cellular structure in the fabrication of foam glass were studied. The fraction of lead released from foam glass was less than those extracted from funnel glass and was lower than the statutory limit. Leached concentrations of barium and strontium were found to be approximately constant in various tests and were also below regulatory limits.

Characterization of self-healing glassy composites by high-temperature environmental scanning electron microscopy (HT-ESEM).

In situ high-temperature healing of cracks in composites made of glass and vanadium boride (VB) particles was observed using an environmental scanning electron microscope equipped with a high-temperature chamber (HT-ESEM). HT-ESEM is an adequate tool for studying the self-healing property of these materials. The change in crack length as a function of redox atmospheric conditions is reported. No self-healing behaviour was observed under reducing conditions, while a complete and rapid healing of the cracks was measured under oxidizing conditions. HT-ESEM image analyses enabled the monitoring of the healing effect. The self-healing mechanism was identified as a consequence of the VB active particles oxidation and subsequent pouring of fluid oxides into the cracks. These innovative composites offer an interesting potential in the domain of solid oxide fuel cell sealants.

Lead extraction from waste funnel cathode-ray tubes glasses by reaction with silicon carbide and titanium nitride.

As a possibility to clean waste CRT glass, treatment of lead-containing glass with a reducing agent, SiC or TiN, leads to a porous material containing metallic lead, Pb(0), located on the surface of the pore, and unreduced lead, Pb(II). The influences of reducing agent content, of the time, and at last of the temperature on lead reduction were analysed. Our investigations have pointed out significant differences as a function of the used reducing agent. CRT glass heat treated with SiC lead to less Pb(0), compared to TiN as shown by X-ray diffraction, and differential scanning calorimetry (DSC). It has been also evidenced that lead reduction occurs on randomized zones inside the sample leading to macroscopic lead beads inside glassy samples. XPS and XAS measurements were also carried out to investigate the local structure of lead and have evidenced a change of role of lead inside the glassy framework in function of the used conditions.

Influence of AlN, TiN and SiC reduction on the structural environment of lead in waste cathode-ray tubes glass: an x-ray absorption spectroscopy study.

This paper reports an x-ray absorption spectroscopy (XAS) analysis of the local structure around lead contained in foam glasses prepared with waste funnel cathode-ray tube glasses (CRT) and three reducing agents AlN, TiN and SiC. The XAS data were collected at the Pb-L(III) edge to measure the influence of the reducing agent concentration on the unreduced lead content present in the glass. XANES spectra have been demonstrated to be a linear combination of both pure metallic lead and funnel glass spectra, with a significant modification of the funnel spectra for the highest contents of reducing agent. We have shown that the average coordination number of lead decreases in the case of TiN and SiC but remains constant in the case of AlN. The coordination number was found to be more affected for TiN than for SiC. Nevertheless, Pb-O bond lengths were determined to be constant close to 2.23 Å whatever the reducing agent and its content.