The potential of the application of an X-ray excited optical luminescence (XEOL) analyzer and portable analyzers, composed of a cathodoluminescence (CL) spectrometer and electron probe microanalyzer (EPMA), to the on-line and on-site analysis of nonmetallic inclusions in steel is investigated as the first step leading to their practical use. MgAl2O4 spinel and Al2O3 particles were identified by capturing the luminescence as a result of irradiating X-rays in air on a model sample containing MgAl2O4 spinel and Al2O3 particles in the size range from 20 to 50 μm. We were able to identify the MgAl2O4 spinel and Al2O3 particles in the same sample using the portable CL spectrometer. In both cases, not all of the particles in the sample were identified because the luminescence intensities of the smaller Al2O3 in particular were too low to detect. These problems could be solved by using an X-ray tube with a higher power and increasing the beam current of the portable CL spectrometer. The portable EPMA distinguished between the MgAl2O4 spinel and Al2O3 particles whose luminescent colors were detected using the portable CL spectrometer. Therefore, XEOL analysis has potential for the on-line analysis of nonmetallic inclusions in steel if we have information on the luminescence colors of the nonmetallic inclusions. In addition, a portable EPMA–CL analyzer would be able to perform on-site analysis of nonmetallic inclusions in steel.

Accurate quantification of the chemical composition of eudialyte group minerals (EGM) with the electron probe microanalyzer is complicated by both mineralogical and X-ray-specific challenges. These include structural and chemical variability, mutual interferences of X-ray lines, in particular of the rare earth elements, diffusive volatility of light anions and cations, and instability of EGM under the electron beam. A novel analytical approach has been developed to overcome these analytical challenges. The effect of diffusive volatility and beam damage is shown to be minimal when a square of 20×20 µm is scanned with a beam diameter of 6 µm at the fastest possible speed, while measuring elements critical to electron beam exposure early in the measurement sequence. Appropriate reference materials are selected for calibration considering their volatile content and composition, and supplementary offline overlap correction is performed using individual calibration factors. Preliminary results indicate good agreement with data from laser ablation inductively coupled plasma mass spectrometry demonstrating that a quantitative mineral chemical analysis of EGM by electron probe microanalysis is possible once all the parameters mentioned above are accounted for.

Identification and accurate characterization of platinum-group minerals (PGMs) is usually a very cumbersome procedure due to their small grain size (typically below 10 µm) and inconspicuous appearance under reflected light. A novel strategy for finding PGMs and quantifying their composition was developed. It combines a mineral liberation analyzer (MLA), a point logging system, and electron probe microanalysis (EPMA).

As a first step, the PGMs are identified using the MLA. Grains identified as PGMs are then marked and coordinates recorded and transferred to the EPMA. Case studies illustrate that the combination of MLA, point logging, and EPMA results in the identification of a significantly higher number of PGM grains than reflected light microscopy. Analysis of PGMs by EPMA requires considerable effort due to the often significant overlaps between the X-ray spectra of almost all platinum-group and associated elements. X-ray lines suitable for quantitative analysis need to be carefully selected. As peak overlaps cannot be avoided completely, an offline overlap correction based on weight proportions has been developed. Results obtained with the procedure proposed in this study attain acceptable totals and atomic proportions, indicating that the applied corrections are appropriate.

On February 2, 1968, R. Fitzgerald, K. Keil, and K.F.J. Heinrich published a seminal paper in Science (159, 528–530) in which they described a solid-state Si(Li) energy dispersive spectrometer (EDS) for electron probe microanalysis (EPMA) with, initially, a resolution of 600 eV. This resolution was much improved over previous attempts to use either gas-filled proportional counters or solid-state devices for EDS to detect X-rays and was sufficient, for the first time, to make EDS a practically useful technique. It ushered in a new era not only in EPMA, but also in scanning electron microscopy, analytical transmission electron microscopy, X-ray fluorescence analysis, and X-ray diffraction. EDS offers many advantages over wavelength-dispersive crystal spectrometers, e.g., it has no moving parts, covers the entire X-ray energy range of interest to EPMA, there is no defocusing over relatively large distances across the sample, and, of particular interest to those who analyze complex minerals consisting of many elements, all X-ray lines are detected quickly and simultaneously.

This article will discuss the importance of Raimond Castaing’s thesis on the genesis of a nondestructive and truly quantitative microanalytical method that assisted the scientific community in moving forward in the development of microanalytical instruments. I will also share with you my recollection of the decades of improvement in the electron probe microanalyzer (EPMA), that has allowed us to reach our present level of instrument sophistication, and I will explore with you my thoughts on the future evolution of this technique. To conclude, I will present the current status of related microanalysis techniques developed under Castaing in Orsay in the 1960s, as Castaing’s interest in microanalysis was not limited to electron probe microanalysis alone.

The development of the electron microprobe by Raymond Castaing provided a great stimulus to materials science at a critical time in its history. For the first time, accurate elemental analysis could be performed with a spatial resolution of 1 µm, well within the dimensions of many microstructural features. The impact of the microprobe occurred across the entire spectrum of materials science and engineering. Contributions to the basic infrastructure of materials science included more accurate and efficient determination of phase diagrams and diffusion coefficients. The study of the microstructure of alloys was greatly enhanced by electron microprobe characterization of major, minor, and trace phases, including contamination. Finally, the electron microprobe has proven to be a critical tool for materials engineering, particularly to study failures, which often begin on a micro-scale and then propagate to the macro-scale with catastrophic results.

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.