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Eingeladener Vortrag
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High repetition rate laser-induced breakdown spectroscopy using acousto-optically gated detection
(2014)
This contribution introduces a new type of setup for fast sample analysis using laser-induced breakdown spectroscopy (LIBS). The novel design combines a high repetition rate laser (up to 50 kHz) as excitation source and an acousto-optical modulator (AOM) as a fast switch for temporally gating the detection of the emitted light. The plasma radiation is led through the active medium of the AOM where it is diffracted on the transient ultrasonic Bragg grid. The diffracted radiation is detected by a compact Czerny-Turner spectrometer equipped with a CCD line detector. Utilizing the new combination of high repetition rate lasers and AOM gated detection, rapid measurements with total integration times of only 10 ms resulted in a limit of detection (LOD) of 0.13 wt.% for magnesium in aluminum alloys. This short integration time corresponds to 100 analyses/s. Temporal gating of LIP radiation results in improved LODs and consecutively higher sensitivity of the LIBS setup. Therefore, an AOM could be beneficially utilized to temporally detect plasmas induced by high repetition rate lasers. The AOM in combination with miniaturized Czerny-Turner spectrometers equipped with CCD line detectors and small footprint diode pumped solid state lasers results in temporally gateable compact LIBS setups.
A dynamical model of a laser induced plasma with axial symmetry is developed to systematically study the effects of the plasma equation of state, radiation transfer, various transport phenomena (viscosity, thermal conductivity, diffusion), and the ablation surface on the observable quantities such as spectra emitted by LIBS plasmas containing multiple species. Theoretical and numerical foundations of the model are described in detail. It is shown that the plasma spectra simulated with the equation of state based on the energy balance that includes the kinetic (thermal) energy, ionization energy, and energy of electronic excitations in atoms and ions differ significantly from the spectra obtained for plasmas modeled in the ideal gas approximation (where only the kinetic energy is included into the energy balance). Various transport phenomena, such as viscosity, diffusion, and thermal conductivity, are shown to have a little effect on the spectra. Radiation losses are proved to have noticeable effects. The effects of various interactions (adhesion, heat exchange, mass inflows) of the evolving plasma with the ablation surface are also illustrated by numerical simulations for typical LIBS plasmas. The model provides a numerical tool to assess various settings for LIBS plasma experiments as well as to interpret experimental data.
A spatial heterodyne spectrometer (SHS) is tested for the first time in combination with laser-induced breakdown spectroscopy (LIBS). The spectrometer is a modified version of the Michelson interferometer in which mirrors are replaced by diffraction gratings. The SHS contains no moving parts and the gratings are fixed at equal distances from the beam splitter. The main advantage is high throughput, about 200 times higher than that of dispersive spectrometers used in LIBS. This makes LIBS-SHS a promising technique for low-light standoff applications. The output signal of the SHS is an interferogram that is Fourier-transformed to retrieve the original plasma spectrum. In this proof-of-principle study, we investigate the potential of LIBS-SHS for material classification and quantitative analysis. Brass standards with broadly varying concentrations of Cu and Zn were tested. Classification via principal component analysis (PCA) shows distinct groupings of materials according to their origin. The quantification via partial least squares regression (PLS) shows good precision (relative standard deviation , 10%) and accuracy (within 6 5% of nominal concentrations). It is possible that LIBS-SHS can be developed into a portable, inexpensive, rugged instrument for field applications.
Plasma diagnostics
(2014)