Evaluation of a Thermoelectric Cooler as a Sample Pre-Treatment Method for Laser-Induced Breakdown Spectroscopy (LIBS) Analysis of Liquid Samples.

In this study, the performance of a thermoelectric cooler (TEC) as a simple and easy-to-assemble freezing instrument has been evaluated. Experiments were carried out using samples with different viscosity ranging from 44.07 to 16 965.80 MPa. The analysis of sodium component of the samples by direct laser irradiation of frozen samples showed emission enhancement and higher signal-to-noise ratio compared to that of liquids. This work also focused on using chemometrics methods such as principal component analysis (PCA) to compare the principal component score separation and clustering pattern between frozen and liquid samples. The PCA was constructed by dividing the samples into two different categories: (i) type (paste, cream, gel, and oil) and (ii) viscosity (more than and less than 10 000 MPa). The frozen samples showed a more established separation and clustering compared to that acquired from the liquid samples. However, poorer clustering pattern of some frozen samples could be due to the heat transfer during laser-sample interaction inducing surface melting and splashing. The average laser-induced breakdown spectroscopy (LIBS) spectra were taken at as many different surface areas as possible to ensure the sample surface always maintain similar freezing temperature. This work showed that the TEC pre-treatment method had improved the LIBS measurement of the liquid samples.