X-rays emission spectrometry

Vol. 133. Particle-Induced X-Ray Emission Spectrometry. By Sven A. E. Johansson, John L. Campbell, and Klas G. Malmqvist... 

Although sophisticated methods may constitute the core methods for certification it is useful to include good, well executed routine methods. In order to further minimize systematic error, a conscious purposeful attempt should be made to get methods and procedures with wide-ranging and different sample preparation steps, including no decomposition as in instrumental neutron activation analysis and particle induced X-ray emission spectrometry. 

Principles and Characteristics Particle-induced X-ray emission spectrometry (PIXE) is a high-energy ion beam analysis technique, which is often considered as a complement to XRF. PIXE analysis is typically carried out with a proton beam (proton-induced X-ray emission) and requires nuclear physics facilities such as a Van der Graaff accelerator, or otherwise a small electrostatic particle accelerator. As the highest sensitivity is obtained at rather low proton energies (2-4 MeV), recently, small and relatively inexpensive tandem accelerators have been developed for PIXE applications, which are commercially available. Compact cyclotrons are also often used. 

Johansson, S.A., Campbell, J.L. Malmqvist, K.G. (1995) Particle-Induced X-Ray Emission Spectrometry (PIXE), John Wiley Sons, New York, Chichester. 

Only arc/spark, plasma emission, plasma mass spectrometry and X-ray emission spectrometry are suitable techniques for qualitative analysis as in each case the relevant spectral ranges can be scanned and studied simply and quickly. Quantitative methods based on the emission of electromagnetic radiation rely on the direct proportionality between emitted intensity and the concentration of the analyte. The exact nature of the relation is complex and varies with the technique it will be discussed more fully in the appropriate sections. Quantitative measurements by atomic absorption spectrometry depend upon a relation which closely resembles the Beer-Lambert law relating to molecular absorption in solution (p. 357 etal.). 

When primary X-rays are directed on to a secondary target, i.e. the sample, a proportion of the incident rays will be absorbed. The absorption process involves the ejection of inner (K or L) electrons from the atoms of the sample. Subsequently the excited atoms relax to the ground state, and in doing so many will lose their excess energy in the form of secondary X-ray photons as electrons from the higher orbitals drop into the hole in the K or L shell. Typical transitions are summarized in Figures 8.35 and 8.36. The reemission of X-rays in this way is known as X-ray fluorescence and the associated analytical method as X-ray fluorescence spectrometry. The relation between the two principal techniques of X-ray emission spectrometry is summarized in Figure 8.37. 

The instruments used in X-ray emission spectrometry reflect the principles set out in Chapter 7. Radiation characteristic of the specimen is produced by electron or radiation bombardment. Monochromatic radiation is then presented to the detector by a diffraction device or by use of a series of narrow bandpass filters. Alternatively pulse height analysis (p. 465) can be applied to a series of pulses which have been generated with a size proportional to the radiation energy. Typical X-ray spectrometry arrangements are shown in Figures 8.40 and 8.41. 

Local composition is very useful supplementary information that can be obtained in many of the transmission electron microscopes (TEM). The two main methods to measure local composition are electron energy loss spectrometry (EELS), which is a topic of a separate paper in this volume (Mayer 2004) and x-ray emission spectrometry, which is named EDS or EDX after the energy dispersive spectrometer, because this type of x-ray detection became ubiquitous in the TEM. Present paper introduces this latter method, which measures the X-rays produced by the fast electrons of the TEM, bombarding the sample, to determine the local composition. As an independent topic, information content and usage of the popular X-ray powder dififaction database is also introduced here. Combination of information from these two sources results in an efficient phase identification. Identification of known phases is contrasted to solving unknown stmctures, the latter being the topic of the largest fiaction of this school. 

External beam photon-induced X-ray emission spectrometry has been used to determine total zinc in soils [246]. 

ICP-AES=inductively coupled plasma-atomic emission spectrometry Mg(N03)3=magnesium nitrate MIBK=methylisobutyl ketone MS=mass spectrometry PIXE=proton-induced X-ray emission spectrometry XRF=X-ray fluorescence analysis WM-AES=wavelength-modulated atomic emission spectrometry... 

Simonoff M, Llabador Y, Hamon C, et al. 1984. Extraction procedure for the determination of trace chromium in plasma by proton-induced X-ray emission spectrometry. Anal Chem 56 454-457. 

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