In this paper, we investigated how to use calibration-free (CF) LIBS to quantitatively analyze hydrogen and deuterium in titanium samples in ambient helium gas. First, the LIBS spectra of two metal titanium samples with hydrogen (H)/deuterium (D) concentration ratios of 1.5 (0.6 : 0.4) and 0.67 (0.4 : 0.6) were obtained by a LIBS experiment set-up. Then, based on the Boltzmann plot of the Ti elements, the plasma electron temperatures of the two samples were determined to be 5746K and 5736K, respectively. The corresponding electron density measured by the Stark broadening profile of Ti II (375.9nm) is 7 × 1015 cm-3 and 7.73 × 1015 cm-3. According to the experimental data, the McWhirter criterion was verified and LIBS plasma was in LTE, so CF-LIBS method can be used to analyze the concentration of hydrogen isotopes. The H/D concentration ratios of the two samples were calculated using free calibration method to be 1.48 and 0.81, and the relative errors were 1.33% and 20.9%, respectively. The experimental results demostrated that laser-induced breakdown spectroscopy combined with the free calibration method can be applied in the quantitative analysis of hydrogen isotope.
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