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A mechanism of non-stoichiometric laser ablation is proposed and experimentally verified for multicomponent alloys. The analysis of four-component bronze samples in various excitation modes and the recorded laser plasma spectra revealed that disproportion of plasma elements during laser evaporation arises from selective evaporation of components at the heating-melting-evaporation stage. Correction coefficients proportional to the work function of the alloy component vapor in the heating-melting-evaporation cycle are calculated for the plasma spectrum. Correction procedure for the spectral lines leads to a good agreement of the measured sample composition with the tabulated data. To check that the proposed approach is universal, aluminum alloys and iron alloys (high-alloy stainless steels) are analyzed. It is found that selective evaporation for aluminum alloys is lower than for bronzes. Evaporation selectivity was insignificant for stainless steels. The proposed mechanism for selective evaporation during laser ablation and correction of the plasma spectrum make it unnecessary to use a standard in the quantitative elemental analysis of complex bronze and aluminum alloy samples.
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Першин et al. (2011) studied this question.
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