Evaluation of the uncertainty of element determination using the energy‐dispersive x‐ray fluorescence technique and the emission–transmission method

A detailed study of the uncertainty quantification procedure for the determination of element mass fractions in a soil matrix by using energy‐dispersive x‐ray fluorescence spectrometry and the emission–transmission method was carried out. The particular case of secondary target excitation with an Mo target and Mo anode x‐ray tube was addressed. The effects of simplification of the theoretical model on the determined mass fractions of elements were studied. The main contributions to the uncertainty were identified and the ways of reducing their magnitude were indicated. The approach was found to be helpful in designing an optimum analytical strategy. It can also be used as guidance for assessing the uncertainty in other modes of x‐ray fluorescence analysis. Copyright © 2003 John Wiley & Sons, Ltd.     

Fluoropolymer‐based clear and white paint coatings composition analysis by X‐Ray fluorescence

A new method for the quantification of organic and inorganic phase fractions was developed for fluoropolymer/acrylic‐blend paints – clear and white paint coatings – on aluminum panels by using wavelength dispersive X‐ray fluorescence spectrometry (WDXRF). The method was developed for clear coat samples (only containing fluoropolymer and acrylic phases) as well as white paint samples by also measuring silica and titanium dioxide levels. Both WDXRF and X‐ray photoelectron spectroscopy (XPS), a surface technique, were investigated. For clear coat samples, we found that WDXRF provided far superior quantitative results to XPS, likely related to the extreme surface sensitivity of XPS, in this case a drawback more than a strength. For white paint samples, the X‐ray fluorescence spectrometry method achieved a relative accuracy typically better than 5% for the organic phases and better than 2% for the inorganic phases, for measurements on 8‐mm diameter samples. Copyright © 2013 John Wiley & Sons, Ltd.     

Literature trends in x‐ray emission spectrometry in the period 1990–2000–a review

A quantitative overview is given of the role that x‐ray emission analysis methods, in their various forms, play in the literature for the period from January 1990 to the end of December 2000. The major sources of information were computerized searches through Chemical Abstracts and Web of Science and, specifically for 1998, a manual search through Analytical Abstracts. Areas that are covered in this review pertain to the recent trends in x‐ray emission spectrometry in general and in some specific techniques such as x‐ray fluorescence analysis, synchrotron radiation‐induced and particle‐induced x‐ray emission, total‐reflection and micro‐x‐ray fluorescence analysis. A brief outline of recent developments in the specific fields is given, with emphasis on the various excitation and detection modes, on different application areas and on relative contributions of different countries and languages to the x‐ray emission spectrometry literature. It appears that environmental monitoring and research continue to be particularly important publication fields for x‐ray spectrometry. Copyright © 2003 John Wiley & Sons, Ltd.     

Improvements of the low‐energy performance of a micro‐focus x‐ray source for XRF analysis with the SEM

X‐ray Fluorescence (XRF) with a scanning electron microscope (SEM) is a valuable completion of the analytical capabilities of SEMs. Small and compact micro‐focus x‐ray sources are mounted to the microscope chamber, and the x‐ray spectra are monitored with conventional EDS systems. Up to now the x‐ray tubes used for the micro‐focus x‐ray sources are equipped with beryllium windows about 100 µm thick. The poly‐capillary x‐ray lenses have their transmission maximum at photon energies around 10 keV. It drops down in both low‐ and high‐energy ranges. Hence, L‐radiation from an Mo or Rh target will be strongly attenuated, and the excitation of fluorescence in the soft x‐ray range becomes very ineffective. A new micro‐focus x‐ray source was developed. It is characterised by a lower self‐absorption in the tube target, thin beryllium windows and an x‐ray optics having a large distance between its foci and the maximum of transmission at about 5 keV. Thus K line fluorescence of light elements becomes effectively excited by the L‐radiation from Mo or Rh tube targets. The detection limit for sodium oxide in glass was found to be below 1 mass%. Copyright © 2009 John Wiley & Sons, Ltd.     

Portable x‐ray fluorescence spectrometer with a pyroelectric x‐ray generator

A portable x‐ray fluorescence spectrometer was assembled with an x‐ray generator that was driven by a 9 V dry electric battery. Several possible optimum geometries of the x‐ray generator and detector were evaluated, and the results showed that the intensity of fluorescent x‐rays was strong enough when the angle between the x‐ray generator and detector was as small as 30°. The geometrically optimized x‐ray spectrometer was applied to the analysis of paints, plastics and aluminum foils. Pigments in paint and toxic elements in plastic could be easily detected with on‐site analysis. Fe in aluminum foil was quantitatively determined down to the sub‐% level. The detection limit of Fe was 180 ppm for 100 s of measurement. Copyright © 2005 John Wiley & Sons, Ltd.     

A new microfocus x‐ray source,iMOXS, for highly sensitive XRF analysis in scanning electron microscopes

Scanning electron microscopes are usually equipped with energy‐dispersive X‐ray detectors for electron probe microanalysis. This widespread analytical method allows investigators to determine the elemental composition of specimens with a spatial resolution of about 1 µm. However, owing to the electron–specimen interaction, the emitted spectra reveal, in addition to characteristic lines, also a high level of continuous bremsstrahlung background. As a result, elements with low concentrations cannot be identified. The minimum detection limit can be diminished by two orders of magnitude if the characteristic lines are excited as fluorescence by an additional x‐ray source. In this case, the emergence of bremsstrahlung is considerably reduced. Combining a high‐brilliance microfocus x‐ray tube with efficient polycapillary optics enables one to realize an experimental arrangement for performing local fluorescence analysis at the same point where the electron beam hits the sample. The polycapillary optics under consideration focuses the emitted x‐radiation onto focal spots between 30 and 100 µm in diameter. Count rates of several thousands cps have been achieved. Elemental maps have been obtained by means of the motorized specimen stage of the microscope. Copyright © 2005 John Wiley & Sons, Ltd.     

XRF法在四川盆地须家河组沉积相研究中的应用

X射线荧光光谱仪在地质样品测定上的应用还不是很广泛,而将X射线荧光光谱法应用到沉积相的研究中则更少。将X射线荧光光谱法(XRF)应用到川中地区上三叠统须家河组二段沉积环境及古气候的识别中,针对四川盆地上三叠统须家河组二段沉积相及沉积环境有争议的问题,特别是须二段地层属于陆相沉积还是海相沉积的问题,采集了四川盆地内四个有代表性地区的须家河组样品,采用X 射线荧光光谱法分析须家河组各段沉积物的元素含量及变化特征,并根据不同相带及沉积环境的元素含量标志,定量分析须家河组沉积相带与沉积环境。研究结果表明： 须家河组二段的Sr/Ba值、Mn/Fe 值和Sr/Ca值均落在陆相沉积的范围内,且与须家河组三-四段的元素含量特征无明显差异,Sr/Cu元素比分析结果表明须家河组沉积时期为温暖—湿润的古气候环境,结果证明四川盆地上三叠统须家河组二段属于温湿气候下的陆相沉积,且与须家河组三-四段沉积环境相类似。X射线荧光光谱法与常规化学分析法实验结果相对误差小于3%,该方法简单易行,为沉积相及沉积环境的识别提供了一种简单、可行且能够定量分析的研究方法。为解决有争议地层沉积相的问题提供了一种较可行的新方法,推动了X射线荧光光谱分析法在地质上的应用。     

Application of high‐energy polarized energy‐dispersive x‐ray fluorescence spectrometry to the determination of trace levels of As,Hg, and Pb in certifiable color additives

Advances in x‐ray fluorescence (XRF) using high‐energy polarized energy‐dispersive (ED)XRF spectrometry (PEDXRF) were applied to the determination of trace As, Hg, and Pb in various color additives subject to batch certification by the U.S. Food and Drug Administration (FDA). The objectives of this study were to simplify sample preparation for quantitative determination of these elements and, if possible, to achieve improved sensitivity and detection limits compared to techniques currently used for certification. PEDXRF was compared with wavelength‐dispersive x‐ray fluorescence spectrometry (WDXRF) and inductively coupled plasma – mass spectrometry (ICP‐MS) for the analysis of trace levels of As, Hg, and Pb in certifiable color additives. For these light matrices, PEDXRF provided better signal‐to‐noise and allowed quantitation in smaller amounts of color additive relative to WDXRF and equal or better precision to ICP‐MS. Determination of these trace elements in a variety of color additives was possible relative to calibrations generated from one color additive using specimens prepared simply by pouring the color additive powder into an XRF sample cup. Published 2016. This article is a U.S. Government work and is in the public domain in the USA     

Quantitative thickness determination using x‐ray fluorescence: application to multiple layers

The fundamental parameter method using x‐ray fluorescence was applied to the quantitative determination of single and multiple layer thicknesses using a compact experimental setup. Focused white‐beam radiation was obtained from a high‐voltage Mo x‐ray tube and the fluorescence spectra were acquired using a Peltier‐cooled Si solid‐state detector. The results show that in the case of single layers the accuracy of the thicknesses obtained is very good whereas for multiple layer structures the agreement is poorer, especially for the thinnest layers. This indicates a possible drawback of the standard‐free thickness determination scheme based on fundamental parameters for complex samples. Copyright © 2004 John Wiley & Sons, Ltd.     

Formation and study of electrospark coatings based on titanium aluminides

Coatings containing Ti-Al intermetallics are fabricated by the electrospark deposition of titanium on aluminum and aluminum on titanium. The microstructure and composition of the grown coatings is studied by scanning electron microscopy, X-ray diffraction, and S-ray microanalysis. It is found that the surface layer formed in argon mostly contains the α-TiAl₃ intermetallic independent of the duration and frequency of discharge pulses. The γ-TiAl and α₂-Ti₃Al phases can be obtained by aluminum deposition on titanium followed by the subsequent deposition of a second titanium layer. Aluminum oxide and titanium nitride are additionally formed during the deposition of electrospark coatings in air.     

Multivariate calibrations for the SR‐TXRF determination of trace concentrations of lead and arsenic in the presence of bromine

A synchrotron radiation source and total reflection x‐ray fluorescence (SR‐TXRF) spectrometry were used for the determination of lead and arsenic in aqueous samples. To overcome the serious spectral interference between the two species and the overlap of another interfering element (bromine), a partial least‐squares regression (PLSR) method was used. The calibration models PLSR2 and PLSR1 were based on the x‐ray fluorescence emission signals (9.550–13.663 keV) for a set of 26 different mixtures containing the elements of interest, lead and arsenic, as well as bromine. The results obtained by PLSR1 and PLSR2 were compared with those obtained by the conventional univariate methodology. In the latter case, the areas of the secondary emission lines (Lβ for lead and Kβ for arsenic) were used to elaborate the analytical curves. The capacity of all optimized models was verified using five synthetic samples (external validation). Subsequently the best model was used to determine lead and arsenic recovery capacities when these metals are retained on two ion‐exchange resins (Dowex 50‐X8 and Dowex 1‐X8). The best multivariate model (PLSR1) allowed the determination of lead and arsenic with root mean square errors of prediction (RMSEPs) of 0.03 and 0.24 mg l^?1, respectively. The reduction of this parameter, with respect to the values obtained by conventional univariate methodology (0.26–0.03 mg l^?1 for lead and 0.30–0.24 mg l^?1 for arsenic), indicates that the proposed multivariate methodology really overcomes the problems associated with spectral interferences and minimizes the influence of an interfering agent (bromine). Copyright © 2005 John Wiley & Sons, Ltd.     

Evaluation of effects of irregular shape on quantitative XRF analysis of metal objects

Quantitative XRF analysis of metal alloys can be obtained by using the general fundamental parameter method based on the comparison of x‐ray line fluorescence intensities with those obtained from reference standard pellets in identical experimental conditions. Corrections for auto absorption and secondary excitation effects are fundamental to obtaining quantitative results. When analyzing a real object with irregular, or at least nonpellet‐shaped, geometry and/or of incorrect positioning, an additional correction factor for x‐ray fluorescence line intensities must be entered. In this paper we review the problem of the contributions to the error specific to an irregular surface or incorrect positioning intrinsic to the fundamental parameter method, in the more enlarged context of considering a real experimental setup in which irradiation and detection angles are not exactly constant, as assumed in the fundamental parameter method. They are accounted for by the corrective irregular shape factors. In principle, these factors must be separately calculated for each value of excitation and characteristic x‐ray energies, and the relative precision in the quantitative determination of elemental concentrations with the fundamental parameter method can be estimated from the relative amplitude of the variation of shape factor values depending on the exciting energy spectrum. One obtains the result that the correction due to irregular shape or incorrect positioning of the object under examination tends to the limit 1, or, more generally, to a constant value independent of the excitation and emission x‐ray energies in the limiting case where the direction of the exciting radiation coincides with that of the detected fluorescence x‐rays. The results of calculations of the relative precision of XRF quantitative analysis are shown for gold‐based alloy objects in some specific cases of surface roughness and positioning of the object. Dispersion around the nominal values for the angles of incoming and outgoing x‐ray directions is assumed as determined by the geometric conditions in two selected instrumental setups. A nominal value of 45° was assumed for both the angles in the first case. In the second case, we considered an irradiation setup where the condition of coincidence for incoming and outgoing x‐ray directions is nearly achieved by employing an annular silicon drift detector (SDD) with a central hole, which allows the passage of the exciting x‐rays. An interesting result obtained in the latter case is that, looking only at the dependence on the irregular shape, an attainable precision on the order of <1‰ can be achieved. In view of the possible applications of quantitative XRF analysis to jewellery, employing SDD detectors capable of very high counting rates should allow a statistical error under the above‐mentioned limit in a reasonably short measuring time. However, concerning the error deriving from intrinsic x‐ray tube instability, an investigation aimed at achieving a stable enough system is still needed. Copyright © 2006 John Wiley & Sons, Ltd.     

GE‐MXRF analysis of multilayer films

Polycapillary x‐ray optics (capillary x‐ray lens) is now popular in x‐ray fluorescence (XRF) analysis. Such an x‐ray lens can collect x‐rays emitted from an x‐ray source in a large solid angle and form a very intense x‐ray microbeam which is very convenient for micro x‐ray fluorescence (MXRF) analysis. In this paper, a new method called grazing exit micro x‐ray fluorescence analysis (GE‐MXRF), which combines an x‐ray lens used to form an intense XRF source was developed and applied in multilayer film analysis. Such a method can give the information of film composition, density, and thickness. Through two‐dimensional scan of the film sample, the information of film uniformity can be acquired; meanwhile, this method is also useful in adjusting experiment condition during the film preparation with metal vapor vacuum arc (MEVVA) source ion implantation. Copyright © 2008 John Wiley & Sons, Ltd.     

EDXRF and TXRF analysis of elemental size distributions and environmental mobility of airborne particles in the city of Riga,Latvia

Airborne particles were investigated in the central part of Riga during October 2000. Mass, black carbon and elemental concentrations of airborne particles were measured on Teflon filters from a dichotomous impactor, which samples fine (<2.5 µm) and coarse (2.5–10 µm) fractions of particles. In order to obtain more detailed information on the size distributions of different elements, a seven‐stage Batelle cascade impactor was used, in which quartz plates treated with silicone grease were utilized as backing for the different stages. Total reflection x‐ray fluorescence (TXRF) and energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry were used for elemental analysis on the quartz plates and Teflon filters. The environmentally mobile part of the fine particle elements in the aerosol was determined by subtraction of x‐ray spectra measured before and after sequential leaching of the aerosol filters. The results of the different measurements show that naturally generated street dust and soil particles are dominant in coarse particles, whereas particles generated by human activities are dominant in the size fraction <0.5 µm. Copyright © 2004 John Wiley & Sons, Ltd.     

XRF analysis of micronutrients in endive grown on soils with sewage sludge

A simple and fast method was developed for the determination of traces of Fe, Mn, Cu, Cr, Ni, Zn and Mo in endive using wavelength‐dispersive x‐ray fluorescence spectrometry. Plants were grown in different sewage sludge compositions for 60 days in greenhouse conditions. Samples were compacted and analyzed after drying, milling and homogenization. The method was validated using certified standard reference materials. The results were compared with those obtained by atomic absorption spectrometry. Good agreement for all elements was obtained. The detection limits were found to be Fe 1, Mn 3, Cu 2, Cr 5, Ni 1, Zn and Mo 3 µg g^?1. These results permitted the evaluation of the potential use of sewage sludge as an agricultural amendment. Copyright © 2003 John Wiley & Sons, Ltd.     

Preparation of calibrating standards for x‐ray fluorescence spectrometry of trace metals in plastics

Convenient x‐ray fluorescent spectrometry was developed for the determination of V, Cr, Co, Ni, Ge and Sb in plastic materials. The calibrating standards were prepared by casting of polyurethane or polyester including a xylene solution of organometallic compounds as a standard. The calibrating disk had a homogeneous elemental distribution and excellent durability. The calibration curves of six elements showed a good linearity of less than 50 mass ppm for V and Ni, 100 mass ppm for Co and Ge, 200 mass ppm for Cr, and 400 mass ppm for Sb. The lower limits of detection (3σ) of the present method were 0.19 mass ppm for V, 0.42 for Cr, 0.24 for Co, 0.18 for Ni, 0.066 for Ge, and 2.1 for Sb. The proposed method has been applied to several different industrial plastics. The quantitative results are in good agreement with those obtained by the AAS method and x‐ray fluorescent spectrometry using the fundamental parameter calculation method. Copyright © 2003 John Wiley & Sons, Ltd.     

Monte Carlo calculation using a personal computer for electron probe microanalysis

Monte Carlo simulation for calculating x‐ray spectra under electron impact is carried out by a personal computer. Reduction of the CPU time by reducing the number of incident electrons for calculation is performed. One of the methods used to reduce the number of incident electrons to obtain the results within an acceptable error is provided. We limit the present report to five typical compounds: an oxide (Al₂O₃), a nitride (TiN), a carbide (Al₄C₃), a light–light element compound (BN), and a heavy–light element compound (PbS). We calculate the relative x‐ray intensity generated from the five compounds listed above with the change of the number of the incident electrons. The calculated x‐ray intensity is then converted into the mass % by the ZAF method. Comparisons are made between the calculation and experiment for Al₄C₃ and PbS. It is found that the present Monte Carlo method is useful for investigating a relationship between the number of incident electrons and the acceptable error. The results of 150 incident electrons can be applied in practical analysis, and the calculation time is less than 2 min. Copyright © 2004 John Wiley & Sons, Ltd.     

Chemical analysis of phosphate rock using different methods—advantages and disadvantages

Many analytical methods are considered for chemical analysis of phosphate rock because the accuracy of analysis is very important. In the present investigations, spectrophotometric and x‐ray spectrometric methods were used to determine P₂O₅ whereas SiO₂, CaO, MgO, Al₂O₃ and Fe₂O₃ were determined by gravimetric and x‐ray spectrometric methods. Volumetric and x‐ray spectrometry methods are necessary for fluorine determination. The investigations revealed that x‐ray spectrometry is a precise and accurate technique, which is cost effective and so better than other methods. Spectrophotometric, volumetric and gravimetric methods are expensive, time consuming and laborious. X‐ray spectrometry is suggested for commercial companies using regular analyses to save chemicals, time and labour and to maintain quality. Copyright © 2006 John Wiley & Sons, Ltd.     

X‐ray absorption and x‐ray fluorescence for the characterization of titanium oxide‐modified HPLC silicas

Titanium oxide grafted on to the surfaces of chromatographic silica was investigated by x‐ray fluorescence (XRF) and x‐ray absorption (XAS) spectroscopy and the latter used before and after the extensive use of this material as a support for reversed‐phase high‐performance liquid chromatography (RP‐HPLC). XRF indicated the formation of a complete 2:1 monolayer whereas XAS suggested the presence of more than one titanium oxide structure. These structures show some slight modification after immobilization of PMOS and use in HPLC. Copyright © 2005 John Wiley & Sons, Ltd.     

Nanoresolution interface studies in thin films by synchrotron x‐ray diffraction and by using x‐ray waveguide structure

In the last years we performed several measurements with synchrotron radiation of several facilities to reveal interesting interface phenomena on the nanoscale. We used both x‐ray diffraction [1] , [2] (XRD) and spectrometry techniques. In this paper, we briefly summarize the results obtained from diffraction measurements, which lead us to our recent grazing incidence x‐ray fluorescence analysis (GIXRF) and extended x‐ray absorption fine structure (EXAFS) experiments. We show how a combination of experimental methods of GIXRF analysis and EXAFS spectroscopy in fluorescence detection with x‐ray standing waves (XSW) technique was applied for the depth profiling of a‐Si/Co/a‐Si layers with nanometer resolution to monitor the growth of CoSi intermetallic phase. The investigated layers were placed into the waveguide structure formed by two Ta films to increase sensitivity and accuracy of the measurements. Copyright © 2009 John Wiley & Sons, Ltd.