Gaseous reference standards of formaldehyde from trioxane.

We have developed a dynamic reference standard of gaseous formaldehyde based on diffusion of the sublimate of trioxane and thermal conversion to formaldehyde in the gas phase. We have also produced a gravimetric standard for formaldehyde in a nitrogen matrix, also by thermal conversion of the sublimate of trioxane. Analysis of the gravimetric standard with respect to the dynamic standard has confirmed the comparability of the static and dynamic gravimetric values.

Facile synthesis of titania nanowires via a hot filament method and conductometric measurement of their response to hydrogen sulfide gas.

Titania nanostructures are of increasing interest for a variety of applications, including photovoltaics, water splitting, and chemical sensing. Because of the photocatalytical properties of TiO2, chemical processes that occur at its surface can be exploited for highly efficient nanodevices. A facile and fast synthesis route has been explored that is free of catalysts or templates. An environmental scanning electron microscopy (ESEM) system was employed to grow titania nanowires (NWs) in a water vapor atmosphere (∼1 mbar) and to monitor the growth in situ. In addition, the growth process was also demonstrated using a simple vacuum chamber. In both processes, a titanium filament was heated via the Joule effect and NWs were found to grow on its surface, as a result of thermal oxidation processes. A variety of nanostructures were observed across the filament, with morphologies changing with the wire temperature from the center to the end points. The longest NWs were obtained for temperatures between ∼730 °C and 810 °C. Typically, they have an approximate thickness of ∼300 nm and lengths of up to a few micrometers. Cross sections prepared by focused-ion-beam milling revealed the presence of a porous layer beneath the NW clusters. This indicates that the growth of NWs is driven by oxidation-induced stresses in the subsurface region of the Ti filament and by enhanced diffusion along grain boundaries. To demonstrate the potential of titania NWs grown via the hot filament method, single NW devices were fabricated and used for conductometric sensing of hydrogen sulfide (H2S) gas. The NW electric resistance was found to decrease in the presence of H2S. Its variation can be explained in terms of the surface depletion model.

Microfabricated planar glass gas chromatography with photoionization detection.

We report the development of a microfabricated gas chromatography system suitable for the separation of volatile organic compounds (VOCs) and compatible with use as a portable measurement device. Hydrofluoric acid etching of 95x95mm Schott B270 wafers has been used to give symmetrical hemi-spherical channels within a glass substrate. Two matching glass plates were subsequently cold bonded with the channels aligned; the flatness of the glass surfaces resulted in strong bonding through van der Waals forces. The device comprised gas fluidic interconnections, injection zone and 7.5 and 1.4m long, 320microm internal diameter capillaries. Optical microscopy confirmed the capillaries to have fully circular channel profiles. Direct column heating and cooling could be achieved using a combination of resistive heaters and Peltier devices. The low thermal conductivity of glass allowed for multiple uniform temperature zones to be achieved within a single glass chip. Temperature control over the range 10-200 degrees C was achieved with peak power demand of approximately 25W. The 7.5m capillary column was static coated with a 2microm film of non-polar dimethylpolysiloxane stationary phase. A standard FID and a modified lightweight 100mW photoionization detector (PID) were coupled to the column and performance tested with gas mixtures of monoaromatic and monoterpene species at the parts per million concentration level. The low power GC-PID device showed good performance for a small set of VOCs and sub ng detection sensitivity to monoaromatics.

Harmonisation of coupled calibration curves to reduce correlated effects in the analysis of natural gas by gas chromatography.

Quantitative analysis of natural gas depends on the calibration of a gas chromatograph with certified gas mixtures and the determination of a response relationship for each species by regression analysis. The uncertainty in this calibration is dominated by variations in the amount of the sample used for each analysis that are strongly correlated for all species measured in the same run. The "harmonisation" method described here minimises the influence of these correlations on the calculated calibration curves and leads to a reduction in the root-mean-square residual deviations from the fitted curve of a factor between 2 and 5. Consequently, it removes the requirement for each run in the calibration procedure to be carried out under the same external conditions, and opens the possibility that new data, measured under different environmental or instrumental conditions, can be appended to an existing calibration database.