Chemical sensors based on a polymer coated quartz crystal microbalance (QCM) generally present poor molecular selectivity for compounds that contain similar functional groups and possess the same chemical properties. This paper shows for the first time that the selectivity and sensitivity of a poly(methyl methacrylate) (PMMA) based QCM sensor can be significantly enhanced for aromatic hydrocarbons by incorporating a plasticizer into the polymer film. The sensor was fabricated by spin coating PMMA onto a quartz crystal, and the influence of plasticizer type and amount on the response was evaluated. It was shown that the hydrocarbon sensitivity of plasticizer-free PMMA is negligible, while the sensitivity of plasticized PMMA was similar to or in some cases greater relative to highly responsive rubbery polymers such as polyisobutylene (PIB). Detection limits of 4.0, 1.5, 0.4, 0.6, and 0.1 ppm were obtained on a PMMA film containing 25% w/w di(2-ethylhexyl) phthalate for benzene, toluene, ethylbenzene, p-xylene, and naphthalene, respectively. We found that at low plasticizer levels (∼10% w/w) the PMMA film was more sensitive toward ethylbenzene and p-xylene over naphthalene when compared to a PIB film under similar measurement conditions. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) measurements were performed to understand the sensing mechanism, and these studies confirmed a higher hydrocarbon uptake by PMMA in the presence of plasticizer. Positron annihilation lifetime spectroscopy (PALS) studies detected variations in the free volume properties of the polymer films as a function of plasticizer content. The accessible free volume as measured by PALS was significantly less in the PMMA films compared to the PIB, and this result correlates favorably with differences in the QCM response pattern. The QCM results have been rationalized in terms of free volume theory which is responsible for the higher hydrocarbon diffusion/sorption with increased plasticizer content.

A flexible strategy to prepare a scalable CO2 absorbent (LAHPs) via encapsulating amino acid salt solutions in a polymer matrix.

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A controlled-release test at the In-Situ Laboratory Project in Western Australia injected 38 tonnes of gaseous CO2 between 336-342 m depth in a fault zone, and the gas was monitored by a wide range of downhole and surface monitoring technologies. Injection of CO2 at this depth fills the gap between shallow release (<25 m) and storage (>600 m) field trials. The main objectives of the controlled-release test were to assess the monitorability of shallow CO2 accumulations, and to investigate the impacts of a fault zone on CO2 migration. CO2 arrival was detected by distributed temperature sensing at the monitoring well (7 m away) after approximately 1.5 days and an injection volume of 5 tonnes. The CO2 plume was detected also by borehole seismic and electric resistivity imaging. The detection of significantly less than 38 tonnes of CO2 in the shallow subsurface demonstrates rapid and sensitive monitorability of potential leaks in the overburden of a commercial-scale storage project, prior to reaching shallow groundwater, soil zones or the atmosphere.Observations suggest that the fault zone did not alter the CO2 migration along bedding at the scale and depth of the test. Contrary to model predictions, no vertical CO2 migration was detected beyond the perforated injection interval. CO2 and formation water escaped to the surface through the monitoring well at the end of the experiment due to unexpected damage to the well's fibreglass casing. The well was successfully remediated without impact to the environment and the site is ready for future experiments.