XRFS

The X-ray fluorescence (XRF) technique has been applied extensively to the determination of macro- and micro-amounts of non-metallic elements in polymers. 

Another example of the application of XRFS is determination of tris(2,3-dibromopropyl) phosphate on the surface of flame-retardant polyester fabrics [28]. The technique involves fabric extraction with an organic solvent followed by solvent analysis by XRF for surface bromine and by high-pressure liquid chromatography (HPLC) for molecular tris(2,3-dibromopropyl) phosphate. The technique has been applied to the determination of hydroxy groups in polyesters [29, 30]. 

X-ray on discs Chemical methods on same discs as used for X-ray analysis Chemical method on powder  

A Polymer not treated with alcoholic potassium hydroxide before analysis, (ppm chlorine). X-ray fluorescence in polymer discs. Average of 2 discs (A) B Polymer treated with alcoholic potassium hydroxide before analysis, X-ray fluorescence in polymer discs. Average of 2 discs (B) (ppm chlorine) Difference between average chlorine contents obtained on potassium hydroxide-treated and untreated samples (B) - (A) (ppm chlorine) 

With n = 1 - 100 and x = 2 (polyethylene terephthalate) or 4 (polybutylene terephthalate) and ester-interchange elastomers of 4-polybutylene terephthalate and 

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Acronyms abound in phofoelecfron and relafed specfroscopies buf we shall use only XPS, UPS and, in Sections 8.2 and 8.3, AES (Auger elecfron specfroscopy), XRF (X-ray fluorescence) and EXAFS (exfended X-ray absorption fine sfmcfure). In addition, ESCA is worth mentioning, briefly. If sfands for elecfron specfroscopy for chemical analysis in which elecfron specfroscopy refers fo fhe various branches of specfroscopy which involve fhe ejection of an elecfron from an atom or molecule. Flowever, because ESCA was an acronym infroduced by workers in fhe field of XPS if is mosf often used to refer to XPS rather than to electron spectroscopy in general. 

Figure 8.21 shows schematically a set of lx, 2s, 2p and 3s core orbitals of an atom lower down the periodic table. The absorption of an X-ray photon produces a vacancy in, say, the lx orbital to give A and a resulting photoelectron which is of no further interest. The figure then shows that subsequent relaxation of A may be by either of two processes. X-ray fluorescence (XRF) involves an elecfron dropping down from, say, fhe 2p orbifal fo fill fhe lx... 

Figure 8.21 The competitive processes of X-ray fluorescence (XRF) and Auger electron emission...

There is an important difference between the two techniques in that photons, produced by XRF, can pass through a relatively large thickness of a solid sample, typically 4000 nm, whereas electrons can penetrate only about 2 nm. This means that AES is more useful in the study of solid surfaces, whereas XRF gives information referring more to the bulk of a solid or liquid. 

In XRF, as in AES, the ejection of the core electron from the atom A to produce the ion A, as illustrated in Figure 8.21, may be by an electron beam of appropriate energy or by X-rays. Much of the early work in XRF employed an electron beam but nowadays an X-ray source is used almost exclusively. 

Figure 8.29 shows two of the more common processes involved in XRF. Comparison with Figure 8.23 illustrating an Auger electron process shows that the same system for labelling energy levels is used in AES and XRF. 

The quanfum yield for XRF decreases as fhe nuclear charge increases and also from K fo L emission. 

There are two further effects on K emission XRF which become more important with decreasing nuclear charge. One is the appearance of weak satellite transitions, to lower wavelengths of the main transitions, occurring in the small proportion of doubly ionized atoms which may be produced by the initial X-ray bombardment. The other is a tendency for some transitions to be broadened into bands, rather than the usual sharp lines, due to the... 

Figure 8.29(b) shows that an L emission XRF spectmm is much more complex than a K emission spectmm. This is illustrated by the L spectmm of gold in Figure 8.31. Apart from those labelled I and p, the transitions fall into three groups, labelled a, p and y, the most intense within each group being Mj, Pi and Yi, respectively.

Electron Microprobe A.na.Iysis, Electron microprobe analysis (ema) is a technique based on x-ray fluorescence from atoms in the near-surface region of a material stimulated by a focused beam of high energy electrons (7—9,30). Essentially, this method is based on electron-induced x-ray emission as opposed to x-ray-induced x-ray emission, which forms the basis of conventional x-ray fluorescence (xrf) spectroscopy (31). The microprobe form of this x-ray fluorescence spectroscopy was first developed by Castaing in 1951 (32), and today is a mature technique. Primary beam electrons with energies of 10—30 keV are used and sample the material to a depth on the order of 1 pm. X-rays from all elements with the exception of H, He, and Li can be detected. 

Electron Beam Techniques. One of the most powerful tools in VLSI technology is the scanning electron microscope (sem) (see Microscopy). A sem is typically used in three modes secondary electron detection, back-scattered electron detection, and x-ray fluorescence (xrf). AH three techniques can be used for nondestmctive analysis of a VLSI wafer, where the sample does not have to be destroyed for sample preparation or by analysis, if the sem is equipped to accept large wafer-sized samples and the electron beam is used at low (ca 1 keV) energy to preserve the functional integrity of the circuitry. Samples that do not diffuse the charge produced by the electron beam, such as insulators, require special sample preparation. 

Wavelength dispersive x-ray fluorescence spectrometric (xrf) methods using the titanium line at 0.2570 nm may be employed for the determination of significant levels of titanium only by carefiil matrix-matching. However, xrf methods can also be used for semiquantitative determination of titanium in a variety of products, eg, plastics. Xrf is also widely used for the determination of minor components, such as those present in the surface coating, in titanium dioxide pigments. 

Instrumental Methods for Bulk Samples. With bulk fiber samples, or samples of materials containing significant amounts of asbestos fibers, a number of other instmmental analytical methods can be used for the identification of asbestos fibers. In principle, any instmmental method that enables the elemental characterization of minerals can be used to identify a particular type of asbestos fiber. Among such methods, x-ray fluorescence (xrf) and x-ray photo-electron spectroscopy (xps) offer convenient identification methods, usually from the ratio of the various metal cations to the siUcon content. The x-ray diffraction technique (xrd) also offers a powerfiil means of identifying the various types of asbestos fibers, as well as the nature of other minerals associated with the fibers (9). 

Barium can also be deterruined by x-ray fluorescence (XRF) spectroscopy, atomic absorption spectroscopy, and flame emission spectroscopy. Prior separation is not necessary. XRF can be appHed directly to samples of ore or products to yield analysis for barium and contaminants. AH crystalline barium compounds can be analy2ed by x-ray diffraction. 

At X-ray fluorescence analysis (XRF) of samples of the limited weight is perspective to prepare for specimens as polymeric films on a basis of methylcellulose [1]. By the example of definition of heavy metals in film specimens have studied dependence of intensity of X-ray radiation from their chemical compound, surface density (P ) and the size (D) particles of the powder introduced to polymer. Have theoretically established, that the basic source of an error of results XRF is dependence of intensity (F) analytical lines of determined elements from a specimen. Thus the best account of variations P provides a method of the internal standard at change P from 2 up to 6 mg/sm the coefficient of variation describing an error of definition Mo, Zn, Cu, Co, Fe and Mn in a method of the direct external standard, reaches 40 %, and at use of a method of the internal standard (an element of comparison Ga) value does not exceed 2,2 %. Experiment within the limits of a casual error (V changes from 2,9 up to 7,4 %) has confirmed theoretical conclusions. 

Our communication describes grain size effect in XRF of powder and powder slurry-like substances in terms of the generalized model ... 

DETERMINATION OF COATINGS THICKNESS BY MEANS OF DESK-TOP XRF SPECTROMETERS... 

Standardized techniques atomic absorption (AAA) and photometric (FMA) of the analysis and designed by us a technique X-Ray fluorescence of the analysis (XRF) for metals definition in air of cities and the working areas of plants to production of non-ferrous metals are applied. The samples of aerosols were collected on cellulose (AFA-HA) and perchlorovinyl (AFA-VP and FPP) filters (Russia). The techniques AAA and FMA include a stage of an acid-temperature ashing of a loaded filter or selective extraction of defined elements from filter by approaching dissolvent. At XRF loaded filters were specimens. 

For exposure of reasons of observable discrepancy of results of the analysis simulated experiment with application synthetic reference samples of aerosols [1]. The models have demonstrated absence of significant systematic errors in results XRF. While results AAA and FMA depend on sort of chemical combination of an elements, method of an ashing of a material and mass of silicic acid remaining after an ashing of samples. The investigations performed have shown that silicic acid adsorbs up to 40 % (rel.) ions of metals. The coefficient of a variation V, describing effect of the indicated factors on results of the analysis, varies %) for Mn and Fe from 5 up to 20, for Cu - from 10 up to 40, for Pb - from 10 up to 70, for Co the ambassador of a dry ashing of samples - exceeds 50. At definition Cr by a method AAA the value V reaches 70 %, if element presences an atmosphere in the form of Cr O. At photometric definition Cr (VI) the value V is equal 40%, when the element is present at aerosols in the form of chromates of heavy metals. 

The complex of the following destmctive and nondestmctive analytical methods was used for studying the composition of sponges inductively coupled plasma mass-spectrometry (ICP-MS), X-ray fluorescence (XRF), electron probe microanalysis (EPMA), and atomic absorption spectrometry (AAS). Techniques of sample preparation were developed for each method and their metrological characteristics were defined. Relative standard deviations for all the elements did not exceed 0.25 within detection limit. The accuracy of techniques elaborated was checked with the method of additions and control methods of analysis. 

Variety of biochemical composition and physical features of milk, as well as compound forms of mineral components foreordain necessity to develop the analytical procedures, in which initial sample state suffers minimum change. Absence of dried milk reference standai ds (RSMs) is an obstacle to use nondestructive XRF for solving the given analytical task. In this communication results of nondestmctive x-ray fluorescence determination of Na, Mg, Al, Si, P, S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr, Zr in dried milk powders of limited mass (less than 2 g), obtained with using plant RSMs to calibrate, ai e discussed. 

The presented results allow an understanding of the effect of inadequacy organic matrix of plant reference standai ds and dried milk on XRF result exactness. In the absence of similar RSMs calibrations, obtained with the help of plant RSMs, may be used for analysis of only non-fat milk powders. Correction on fat content will allow a spreading these calibrations on analysis of milk powders with any fat contents. 

X-ray fluorescence (XRF) analysis is successfully used to determine chemical composition of various geological and ecological materials. It is known that XRF analysis has a high productivity, acceptable accuracy of results, developed theory and industrial analytical equipment sets. Therefore the complex methods of XRF analysis have to be constituent part of basis data used in ecological and geochemical investigations... 

The method of XRF silicate analysis has a State certificate of Ukraine. Fstablished errors of XRF silicate analysis data are allow using its results in broad problem fields of geochemical and ecological investigations. 

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