A reflection mode fiber optic oxygen sensor that can operate at high temperatures for power plant applications is being developed. The sensor is based on the {sup 3}O{sub 2} quenching of the red emission from hexanuclear molybdenum chloride clusters. Alkali salts of Mo{sub 6}Cl{sub 12} were synthesized and heated to 280 C for one hour in air. Optical measurements of the thermally treated material confirm the potential of the salts as lumophores in high temperature fiber optic sensors. In addition sol-gel films containing Mo{sub 6}Cl{sub 12} were dip coated on quartz substrates and heated at 200 C for one hour. Conditions were developed for successfully immobilizing monomeric complexes that are compatible with sol-gel processing.

A reflection mode fiber optic oxygen sensor is being developed that can operate at high temperatures for power plant applications. The sensor is based on the {sup 3}O{sub 2} quenching of the red emission from hexanuclear molybdenum chloride clusters. Two critical materials issues are the cluster's ability to withstand high temperatures when immobilized in a porous the sol-gel support, and whether after heating to high temperatures, the sol-gel matrix maintains a high and constant permeability to oxygen to support rapid quenching of luminescence. We used a composite materials approach to prepare stable sensing layers on optical fibers. We dispersed 60 w/w% of a pre-cured sol-gel composite containing the potassium salt of molybdenum clusters (K{sub 2}Mo{sub 6}Cl{sub 14}) into a sol-gel binder solution, and established the conditions necessary for deposition of sol-gel films on optical fibers and planar substrates. The fiber sensor has an output signal of 5 nW when pumped with an inexpensive commercial 365 nm ultraviolet light emitting diode (LED). Quenching of the sensor signal by oxygen was observed up to a gas temperature of 175 C with no degradation of the oxygen permeability of the composite after high temperature cycling. On planar substrates the cluster containing composite responds …

Mo{sub 6}Cl{sub 12}, a cluster compound whose luminescence depends on the ambient concentration of oxygen, is the basis for a real-time oxygen sensor for combustion applications. Previously, the properties of Mo{sub 6}Cl{sub 12} have largely been studied at room temperature; these studies have now been extended to 200 C. Optical microscopy shows that Mo{sub 6}Cl{sub 12} undergoes a steady change in color as it is heated from room temperature to 200 C, changing from canary yellow to crimson and then back to canary yellow. Concurrent thermal gravimetric analyses show a small weight loss for Mo{sub 6}Cl{sub 12} that is consistent with loss of water or HCl from the clusters. These changes are reversible. Absorption and fluorescence emission spectroscopy of Mo{sub 6}Cl{sub 12} heated to 200 C for two hours shows no change in the photophysical parameters compared to the control sample that was not heat cycled.