Electron microprobe X-ray emission spectrometry

This is very much a specialised method, but is very useful for the identification of small inclusions in solids. The basic instrument is an electron microscope, but all or part of the electron beam can be focused onto any desired part of the sample causing it to emit X-rays characteristic of that material. These are then collimated and analysed in a conventional X-ray fluorescence spectrograph, thus giving at least a partial ratio analysis of that part of the sample. These instruments are expensive and are not for routine analysis, but are very useful for the identification of small problem areas in solid materials. 

Energy dispersive measuring devices are most commonly used. Interference effects do occur, which are chiefly caused by fluorescent emissions and matrix defects. Corrections can be made. 

Auger electron, electron energy loss, and X-ray photoelectron spectroscopies are related methods suitable for the determination of elements with atomic numbers down as far 

Electron probe microanalysis has been used for the identification of metallic inclusions in polymer film and sheet. The sample is bombarded with a very narrow beam of X-rays of known frequency and the backscattered electron radiation is examined. An image is produced of the distribution of elements of any particular atomic numbers. 

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The surface of the particles can be studied directly by the use of electron microprobe X-ray emission spectrometry (EMP), electron spectroscopy for chemical analysis (ESCA), Auger electron spectroscopy (AES), and secondary ion-mass spectrometry. Depth-profile analysis determines the variation of chemical composition below the original surface. 

The analysis of metals by X-ray fluorescence has been widely used on geological and sediment samples, either deposited on filters or as thin films. The method can be made quantitative by using geological standards and transition metals can be determined in the 1-5 tg per g range. The surfaces of sediment particles can be examined by the direct use of electron microprobe X-ray emission spectrometry and Auger electron spectroscopy. Although these methods are not particularly sensitive, they can allow the determination of a depth-profile of trace metals within a sediment particle. 

Impurity inclusions and surface defects are a cause of many difficulties to the polymer producer and user. Equipment used for studying these phenomena discussed in Chapter 4 include electron microprobe x-ray emission/spectroscopy, NMR micro-imaging, various forms of surface infrared spectroscopy, e.g., diffusion reflection FTIR, ATR, also photoacoustic spectroscopy and x-ray diffraction - infrared microscopy of individual polymer fibres. Newer techniques such as scanning electron microscopy (SECM), transmission electron microscopy, time of flight secondary ion mass spectrometry (TOFSIMS), laser induced photoelectron ionisation with laser desorption, atomic force microscopy and microthermal analysis are discussed. 

Elemental chemical analysis provides information regarding the formulation and coloring oxides of glazes and glasses. Energy-dispersive x-ray fluorescence spectrometry is very convenient. However, using this technique the analysis for elements of low atomic numbers is quite difficult, even when vacuum or helium paths are used. The electron-beam microprobe has proven to be an extremely useful tool for this purpose (106). Emission spectroscopy and activation analysis have also been appHed successfully in these studies (101). 

Neutron Activation Analysis X-Ray Fluorescence Particle-Induced X-Ray Emission Particle-Induced Nuclear Reaction Analysis Rutherford Backscattering Spectrometry Spark Source Mass Spectrometry Glow Discharge Mass Spectrometry Electron Microprobe Analysis Laser Microprobe Analysis Secondary Ion Mass Analysis Micro-PIXE... 

There are two principal sources of reliable partitioning data for any trace element glassy volcanic rocks and high temperature experiments. For the reasons outlined above, both sources rely on analytical techniques with high spatial resolution. Typically these are microbeam techniques, such as electron-microprobe (EMPA), laser ablation ICP-MS, ion-microprobe secondary ion mass spectrometry (SIMS) or proton-induced X-ray emission (PIXE). 

There are now several different types of machines that are all capable of microanalysis. All have advantages and disadvantages, but the choice of which to use is often governed by expense and availability to a particular institution. Electron probe microanalysis is by far the most popular, but here particle-induced X-ray emission (PIXE), the laser microprobe mass analyzer (LAMMA), electron energy loss spectroscopy (EELS), and secondary ion mass spectrometry (SIMS) are also considered. 

XRD, X-ray diffraction XRF, X-ray fluorescence AAS, atomic absorption spectrometry ICP-AES, inductively coupled plasma-atomic emission spectrometry ICP-MS, Inductively coupled plasma/mass spectroscopy IC, ion chromatography EPMA, electron probe microanalysis SEM, scanning electron microscope ESEM, environmental scanning electron microscope HRTEM, high-resolution transmission electron microscopy LAMMA, laser microprobe mass analysis XPS, X-ray photo-electron spectroscopy RLMP, Raman laser microprobe analysis SHRIMP, sensitive high resolution ion microprobe. PIXE, proton-induced X-ray emission FTIR, Fourier transform infrared. 

Microprobe techniques, and their detection limits (given in mgkg ), that have been applied to Al localization include energy dispersive (electron probe) X-ray microanalysis (20), wavelength-dispersive X-ray microanalysis, electron energy loss spectrometry (500), proton probe nuclear microscopy (10), resonance ionization mass spectrometry (3), secondary ion mass spectrometry (1), laser microprobe mass spectrometry (1) and micropartide-induced X-ray emission (Yokel 2000). 

A wide range of analytical techniques is necessary to provide an unambiguous identification of pigments in a sample. Elemental techniques are often used, such as scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), X-ray fluorescence (XRE) spectrometry, scanning electron microprobe analysis (EPMA), X-ray photoelectron spectroscopy (XPS), particle-induced X-ray emission (PDCE), neutron activation analysis (NAA), atomic absorption spectrometry (AAS), inductively coupled... 

Direct determination of solids may be performed by, e.g.. X-ray fluorescence spectrometry, or by arc or spailr emission spectrometry in case of powders. For special applications many surface techniques are available such as proton-induced X-ray emission (PIXE) and laser microprobe emission spectrometry (LMA). In the case of determination of trace elements on clinical material, however, most of these direct methods have detection limits that are too high to be useful. Moreover, as some of these methods are cormected to an accelerator or electron microscope, usage is somewhat limited for routine determination. 

Every effort is made here to achieve the highest possible absolute power of detection. Microdistribution analysis represents the primary field of application for microprobe techniques based on beams of laser photons, electrons, or ions, including electron microprobe analysis (EPMA), electron energy-loss spectrometry (EELS), particle-induced X-ray spectrometry (PIXE), secondary ion mass spectrometry (SIMS), and laser vaporization (laser ablation). These are exploited in conjunction with optical atomic emission spectrometry and mass spectrometry, as well as various forms of laser spectrometry that are still under development, such as laser atomic ab.sorption spectrometry (LAAS), resonance ionization spectrometry (RIS). resonance ionization mass spectrometry (RIMS), laser-enhanced ionization (LEI) spectrometry, and laser-induced fluorescence (LIF) spectrometry [36]-[44],... 

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