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This article is a detailed account of the principles of electron-excited X-ray microanalysis. It begins by discussing the physical basis of electron-excited X-ray microanalysis and the advantages and limitations of energy dispersive spectrometry (EDS) and wavelength dispersive spectrometry for electron probe microanalysis. Key concepts for performing qualitative analysis and quantitative analysis by electron-excited X-ray spectrometry are then presented. Several sources that lead to measurement uncertainties in the k-ratio/matrix corrections protocol are provided, along with the significance of the raw analytical total. Sections on accuracy of the standards-based k-ratio/matrix corrections protocol with EDS and processes of analysis when severe peak overlap occurs are also included. The article provides information on low-atomic-number elements, iterative qualitative-quantitative analysis for complex compositions, and significance of standardless analysis in the EDS software. It ends with a section on the processes involved in elemental mapping for major and minor constituents.

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