The experimental evaluation of the Rhodes–Hunuer model of the particle size effect in X‐ray fluorescence analysis of ‘thin’ and monolayer samples is reported. The calculations and experiments were carried out for samples of iron oxide(Fe3O4) and copper sulphide (Cu2S) having particles of one size and a histog am distribution of particle sizes. For iron oxide particles, it was found that sticking causes a significant systematic discrepancy between the experimental results and the Rhodes–Hunter model prediction. For copper sulphide particles the model was applicable.
A method of correction for the particle‐size effect in the x‐ray fluorescence analysis of thin and monolayer samples is proposed. The method consists of the measurement of characteristic x‐rays excited by x or γ radiation of two different energies. A concept of a substitute radiometric particle diameter instead of the particle‐size distribution has been introduced in order introduced in order to enable a practical application of the proposed method. The particle‐size correction factors have been obtained theoretically and experimentally for iron oxide (Fe3O4), calcium sulphate (CaSO4) and copper sulphide (Cu2S) with various particle‐size distributions. The application limits of the proposed method have been discussed.
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