Standardless Quantitative Electron-Excited X-ray Microanalysis by Energy-Dispersive Spectrometry: What Is Its Proper Role?

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.