Unification of fundamental matrix correction methods in X-ray fluorescence analysis. Arguments for a new binary coefficient approach

A comparative study of the main fundamental approaches for mathematical matrix correction in x‐ray fluorescence analysis is proposed. It shows that the fundamental parameter method (Criss and co‐workers) and the competing fundamental coefficient methods (Broll, Rousseau, Tertian) are in principle equivalent, then convergent as to their results, and suffer from the same inherent limitations. Authors differ as to the ways in which these shortcomings can be overcome or greatly reduced (essentially owing to standards), and these practical aspects are also discussed in detail. The paper recalls the many advances achieved with regard to the comprehension of influence coefficients (binary coefficients, effective multicomponent coefficients, interpretation of third element effects). As a consequence, it is shown that the utilization of accurate binary coefficients, combined with a single fundamental parameter calculation of the relative intensities for the sample, results in a very favourable algorithm. Theoretically equivalent to the former formulations, it is definitely simpler as regards the calculation scheme, and more general with regard to the scope of applications. It is best suited for the experimental control of instrumental factors.