Electron beam X-ray microanalysis with semiconductor energy-dispersive
spectrometry (EDS) performed with standards and calculated matrix
corrections can yield quantitative results with a distribution such that
95% of analyses fall within ±5% relative for major and minor
constituents. Standardless methods substitute calculations for the
standard intensities, based either on physical models of X-ray generation
and propagation (first principles) or on mathematical fits to remotely
measured standards (fitted standards). Error distributions have been
measured for three different standardless analysis procedures with a suite
of microanalysis standards including metal alloys, glasses, minerals,
ceramics, and stoichiometric compounds. For the first-principles
standardless procedure, the error distribution placed 95% of analyses
within ±50% relative, whereas for two commercial fitted standards
procedures, the error distributions placed 95% of analyses within
±25% relative. The implication of these error distributions for the
accuracy of analytical results is considered, and recommendations for the
use of standardless analysis are given.