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.

This article discusses the capabilities and limitations of various material characterization methods that assist in the selection of a proper analytical tool for analyzing particulate materials. Commonly used methods are microanalysis, surface analysis, and bulk analysis. The techniques used for performing microanalysis include scanning electron microscopy and electron probe X-ray microanalysis. The article describes surface analysis techniques, including Auger electron spectroscopy, X-ray photoelectron spectroscopy, and ion-scattering spectroscopy. Bulk analysis techniques, such as X-ray powder diffraction, inductively coupled plasma atomic emission spectroscopy, atomic absorption spectroscopy, and atomic fluorescence spectrometry, are also discussed.

Electron probe microanalysis (EPMA) makes it possible to combine structural and compositional analysis in one operation. This article describes the basic concepts of microanalysis and the processing of EPMA that involves the measurement of the characteristic X-rays emitted from a microscopic part of a solid specimen bombarded by a beam of accelerated electrons. It provides information on the various aspects of energy-dispersive spectrometry (EDS) and wavelength-dispersive spectrometry (WDS), and elucidates the qualitative analysis of the major constituents of EDS and WDS. The article includes information on the analog and digital compositional mapping of elemental distribution, and describes the strengths and weaknesses of WDS and EDS spectrometers in X-ray mapping. It also outlines the application of EPMA for solving various problems in materials science.