The impact of water and hydrocarbon concentration on the sensitivity of a polymer-based quartz crystal microbalance sensor for organic compounds

Long-term environmental monitoring of organic compounds in natural waters requires sensors that respond reproducibly and linearly over a wide concentration range, and do not degrade with time. Although polymer coated piezoelectric based sensors have been widely used to detect hydrocarbons in aqueous solution, very little information exists regarding their stability and suitability over extended periods in water. In this investigation, the influence of water aging on the response of various polymer membranes polybutadiene (PB), polyisobutylene (PIB), polystyrene (PS), polystyrene-co-butadiene (PSB)] was studied using the quartz crystal microbalance (QCM). QCM measurements revealed a modest increase in sensitivity towards toluene for PB and PIB membranes at concentrations above 90 ppm after aging in water for 4 days. In contrast, the sensitivity of PS and PSB coated QCM sensors depended significantly on the toluene concentration and increased considerably at concentrations above 90 ppm after aging in water for 4 days. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR–FTIR) showed that there is a change in the sorption mechanism at higher toluene levels for PS and PSB. Positron annihilation lifetime spectroscopy (PALS) studies were performed to investigate the free volume properties of all polymers and to monitor any changes in the free volume size and distribution due to water and toluene exposure. The PALS did not detect any considerable variation in the free volume properties of the polymer films as a function of solution composition and soaking time, implying that viscoelastic and/or interfacial processes (i.e. surface area changes) are probably responsible for variations in the QCM sensitivity at high hydrocarbon concentrations. The results suggest that polymer membrane conditioning in water is an issue that needs to be considered when performing QCM measurements in the aqueous phase. In addition, the study shows that the hydrocarbon response is concentration dependant for polymers with a high glass transition temperature, and this feature is often neglected when comparing sensor sensitivity in the literature.