A peak‐to‐background (P/B) method was implemented for standardless analysis of bulk samples. Components of the model were selected from the literature on the basis of comparison with the present experimental results. Pouchou and Pichoir's characteristic x‐ray intensity calculations combined with Small et al. bremsstrahlung model proved to be the most successful in this respect. An empirical modification seems to be necessary to improve the agreement between calculated and measured P/Bs for the Lα lines of single‐element samples. For modelling the dependence of the measured P/B on the particle size, small particles are approximated as thin layers. Preliminary experimental results illustrate that even such a rough approximation works.
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