Investigation of the afterglow time regime in pulsed radiofrequency glow discharge time-of-flight mass spectrometry.

The pulsed power operation mode of a radiofrequency (rf) glow discharge time-of-flight mass spectrometer was investigated, for several ions, in terms of intensity profiles along each pulse period. Particular attention was paid to the plateau and transient afterglow regions. An rf pulse period of 4 ms and a duty cycle of 50% was selected to evaluate the influence of discharge parameters in the afterglow delay and shape of Ar(+), Ar(2)(+) and several analytes (Br, Cl, Cu) contained in polymeric layers. Pulse shapes of Ar(+) and Ar(2)(+) ions vary with pressure and power. At low pressures the highest intensity is observed in the plateau while at higher pressures (>600 Pa) the afterpeak is the dominant region. Although the influence of the applied power is less noticeable, a widening of the afterglow time regime occurs for Ar(+) when increasing the power. Maximum intensity of the argon signal is measured in the afterglow at 30 W, while the area of such afterpeak increases with power. The maximum intensity of Ar(2)(+) is obtained at the highest power employed (60 W) and the ratio maximum intensity/afterglow area remains approximately constant with power. Analytes with ionization potentials below (Cu) or just above (Br) the argon metastable energy show maxima intensities after argon ions decay, indicating they could be ionized by collisions with metastable Ar atoms. Chlorine signals are observed in the afterglow despite their ionization potential is well above the energy of argon metastable levels. Moreover, they follow a similar pattern to that observed for Ar(2)(+) , indicating that charge-transfer process with Ar(2)(+) could play a significant role.

Analysis of small bubbles in glass by glow discharge--time-of-flight mass spectrometry.

The chemical reactions occurring during the glass manufacturing processes can give rise to small bubbles, damaging the required glass properties. To avoid eventual bubbles formation, the chemical composition of the bubbles should be known to trace back the gas sources and take appropriate corrective actions. Mass spectrometry is a most adequate detection technique for such purpose due to its ability to provide the required information in a short time. Analysis of these small bubbles in glass requires a system incorporating a very small volume (for a fast evacuation of the entire line and low dilution of the analytes) and a fast mass analyser allowing the quasi-simultaneous detection of the whole spectral interval of interest, such as a time-of-flight mass spectrometer (TOFMS). In this work, the analytical potential of a radiofrequency glow discharge (rf-GD) coupled to a TOFMS was evaluated for the first time for the analysis of bubbles in glasses. The operating conditions of the rf-GD (pressure and applied power) were optimized by introducing into the system known volumes of air. Detection limits in the order of nL were obtained for molecular nitrogen, oxygen and carbon dioxide. Finally, a stainless steel bellows valve was modified to serve as glass breaker for the sampling process. This valve was connected on-line to the mass spectrometer inlet line and proved to be most appropriate for the analysis of the gaseous content of bubbles (with diameters below 0.5mm) entrapped in industrial glasses.