Simulation of layer measurement with confocal micro‐XRF

A simple model to simulate the measurement of layered structures with confocal micro X‐ray fluorescence (micro‐XRF) was developed and implemented as a computer program. The model assumes monochromatic excitation, considers at the moment only K lines, and simplifies the volume defined by excitation and detection foci as a circle area. First simulation results and comparison with data acquired using the Atominstitut confocal micro‐XRF spectrometer are very promising. The simulation software enables us to perform parameter studies to have a better understanding of the analysis of layered structures with confocal micro‐XRF. Copyright © 2014 John Wiley & Sons, Ltd.     

毛细管X光透镜三维共聚焦微束X射线荧光技术在岩矿样品分析中的应用

利用毛细管X光透镜搭建了三维共聚焦微束X射线荧光谱仪,处在激发道的多毛细管X射线会聚透镜和处在探测道的多毛细管X射线平行束透镜处于共聚焦状态,该共聚焦结构降低了X射线荧光光谱的背底,从而有利于降低的X射线荧光分析技术的探测极限。在上述共聚焦结构中,多毛细管X射线会聚透镜和多毛细管X射线平行束透镜的焦斑重合形成共聚焦微元,探测器只能探测到来自该共聚焦微元内的X射线荧光信号,当该共聚焦微元在样品移动时,就可利用该共聚焦技术原位无损得到样品内部的三维X射线荧光信息。该共聚焦技术使用的多毛细管X射线会聚透镜具有103量级的功率放大倍数,从而降低了该共聚焦技术对高功率X射线源的依赖程度,即利用低功率普通X射线源就可以设计毛细管X光透镜共聚焦X射线荧光技术。利用上述共聚焦微束X射线荧光谱仪对两种岩矿样品进行三维无损分析,在其中一种岩石中发现：Fe浓度大的区域Cu的浓度也大,这在一定程度上反映了岩矿自然生长的机理。实验结果证明：该共聚焦X射线荧光技术可以在不破坏样品情况下分析岩矿样品中元素成分组成和元素三维分布情况。该共聚焦三维微束X射线荧光技术在矿石勘察、玉器选材和鉴别、石质食用器皿、“赌石”和家用石质地板检测等领域具有潜在的应用。     

Application of Three Dimensional Confocal Micro X-Ray Fluorescence Technology Based on Polycapillary X-Ray Lens in Analysis of Rock and Mineral SamplesSCIEI北大核心CSCD

Confocal three dimensional (3D) micro X-ray fluorescence (XRF) spectrometer based on a polycapillary focusing X-ray lens (PFXRL) in the excitation channel and a polycapillary parallel X-ray lens (PPXRL) in the detection channel was developed. The PFXRL and PPXRL were placed in a confocal configuration. This was helpful in improving the signal-to-noise ratio of the XRF spectra, and accordingly lowered the detection limitation of the XRF technology. The confocal configuration ensured that only the XRF signal from the confocal micro-volume overlapped by the output focal spot of the PFXRL and the input focal spot of the PPXRL could be detected by the detector. Therefore, the point-to-point information of XRF for samples could be obtained non-destructively by moving the sample located at the confocal position. The magnitude of the gain in power density of the PFXRL was 10(3). This let the low power conventional X-ray source be used in this confocal XRF, and, accordingly, decreased the requirement of high power X-ray source for the confocal XRF based on polycapillary X-ray optics. In this paper, we used the confocal 3D micro X-ray fluorescence spectrometer to non-destructively analyzed mineral samples and to carry out a 3D point-to-point elemental mapping scanning, which demonstrated the capabilities of confocal 3D micro XRF technology for non-destructive analysis elements composition and distribution for mineral samples. For one mineral sample, the experimental results showed that the area with high density of element of iron had high density of copper. To some extent, this reflected the growth mechanisms of the mineral sample. The confocal 3D micro XRF technology has potential applications in such fields like the analysis identification of ore, jade, lithoid utensils, "gamble stone" and lithoid flooring.     

Comparison of the detection limits in the analysis of some medium atomic number elements measured with a portable XRF and an external proton beam PIXE spectrometer system

A portable X‐ray fluorescence (XRF) spectrometer system was constructed using an Amptek Mini‐X X‐ray tube and an X‐123 compact spectrometer. The spectrometer is optimised for the best limits of detection. Its analytic properties are tested and compared with an analogous laboratory‐based instrument, an external beam proton‐induced X‐ray emission spectrometry (PIXE) setup. Depending on elements in question the thick target detection limits of this portable XRF device are comparable or even lower than the PIXE setup. Copyright © 2011 John Wiley & Sons, Ltd.     

Depth‐selective elemental imaging of microSD card by confocal micro XRF analysis

A semiconductor device, a microSD card, was measured by using two XRF instruments. 2D elemental images were obtained using a micro‐XRF system with a spatial resolution of 10 µm. Elemental distributions of the near‐surface region of the sample were clearly shown. Titanium was observed in the resin constituting the sample. Nickel and gold were observed on a terminal and localization of the sample. Elemental distribution of copper reflected the circuit structure of the measurement area that was in the neighborhood of the sample surface. Moreover, the elemental depth distributions of the sample were measured by using a confocal micro‐XRF instrument. The confocal micro‐XRF instrument was constructed in the laboratory with fine‐focus polycapillary x‐ray optics. The depth resolution of the developed spectrometer was 13.7 µm at an energy of Au Lβ (11.4 keV). The elemental images obtained at near‐surface by confocal micro‐XRF were the same as the results obtained from 2D micro‐XRF. However, different Cu images were obtained at a depth of several tens of micrometers. This indicates that microSD cards consist of a few different Cu‐circuit structure designs. The elemental depth distributions of each circuit structure of the semiconductor device were clearly shown by confocal micro‐XRF. Copyright © 2013 John Wiley & Sons, Ltd.     

Monte Carlo simulation code for confocal 3D micro‐beam X‐ray fluorescence analysis of stratified materials

Stratified materials are of great importance for many branches of modern industry, e.g. electronics or optics and for biomedical applications. Examination of chemical composition of individual layers and determination of their thickness helps to get information on their properties and function. A confocal 3D micro X‐ray fluorescence (3D µXRF) spectroscopy is an analytical method giving the possibility to investigate 3D distribution of chemical elements in a sample with spatial resolution in the micrometer regime in a non‐destructive way. Thin foils of Ti, Cu and Au, a bulk sample of Cu and a three‐layered sandwich sample, made of two thin Fe/Ni alloy foils, separated by polypropylene, were used as test samples. A Monte Carlo (MC) simulation code for the determination of elemental concentrations and thickness of individual layers in stratified materials with the use of confocal 3D µXRF spectroscopy was developed. The X‐ray intensity profiles versus the depth below surface, obtained from 3D µXRF experiments, MC simulation and an analytical approach were compared. Correlation coefficients between experimental versus simulated, and experimental versus analytical model X‐ray profiles were calculated. The correlation coefficients were comparable for both methods and exceeded 99%. The experimental X‐ray intensity profiles were deconvoluted with iterative MC simulation and by using analytical expression. The MC method produced slightly more accurate elemental concentrations and thickness of successive layers as compared to the results of the analytical approach. This MC code is a robust tool for simulation of scanning confocal 3D µXRF experiments on stratified materials and for quantitative interpretation of experimental results. Copyright © 2011 John Wiley & Sons, Ltd.     

Nondestructive elemental depth profiling of Japanese lacquerware ‘Tamamushi‐nuri’ by confocal 3D‐XRF analysis in comparison with micro GE‐XRF

We have applied recently two XRF (micro x‐ray fluorescence) methods [micro‐Grazing Exit XRF (GE‐XRF) and confocal 3D‐XRF] to Japanese lacquerware ‘Tamamushi‐nuri.’ A laboratory grazing‐exit XRF (GE‐XRF) instrument was developed in combination with a micro‐XRF setup. A micro x‐ray beam was produced by a single capillary and a pinhole aperture. Elemental x‐ray images (2D images) obtained at different analyzing depths by micro GE‐XRF have been reported. However, it was difficult to directly obtain depth‐selective x‐ray spectra and 2D images. A 3D XRF instrument using two independent polycapillary x‐ray lenses and two x‐ray sources (Cr and Mo targets) was also applied to the same sample. 2D XRF images of a Japanese lacquerware showed specific distributions of elements at the different depths, indicating that ‘Tamamushi‐nuri’ lacquerware has a layered structure. The merits and disadvantages of both the micro GE‐XRF and confocal micro XRF methods are discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

A simple calibration procedure of polycapillary based portable micro‐XRF spectrometers for reliable quantitative analysis of cultural heritage materials

Portable micro‐X‐ray fluorescence (micro‐XRF) spectrometers mostly utilize a polycapillary X‐ray lens along the excitation channel to collect, propagate and focus down to few tens of micrometers the X‐ray tube radiation. However, the polycapillary X‐ray lens increases the complexity of the quantification of micro‐XRF data because its transmission efficiency is strongly dependent on the lens specifications and the propagated X‐ray energy. This feature results to a significant and not easily predicted modification of the energy distribution of the primary X‐ray tube spectrum. In the present work, we propose a simple calibration procedure of the X‐ray lens transmission efficiency based on the fundamental parameters approach in XRF analysis. This analytical methodology is best suited for compact commercial and portable micro‐XRF spectrometers. The developed calibration procedure is validated through the quantitative analysis of a broad range of samples with archeological relevance such as glasses, historical copper alloys, silver and gold alloys offering an overall accuracy of less than 10%–15%. Copyright © 2015 John Wiley & Sons, Ltd.     

Integrating 3D images using laboratory‐based micro X‐ray computed tomography and confocal X‐ray fluorescence techniques

The application of non‐destructive imaging to characterizing samples has become more important as the costs of samples increase. Imaging a sample via X‐ray techniques is preferable when altering or even touching the sample affects its properties, or when the sample is fielded after characterization. Two laboratory‐based X‐ray techniques used at Los Alamos include micro X‐ray computed tomography (MXCT) and confocal micro X‐ray fluorescence (confocal MXRF). Both methods create a 3D rendering of the sample non‐destructively. MXCT produces a high‐resolution (sub‐µm voxel) rendering of the sample based upon X‐ray absorption; the resulting model is a function of density and does not contain any elemental information. Confocal MXRF produces an elementally specific 3D rendering of the sample, but at a lower (30 × 30 × 65 µm) resolution. By combining data from these two techniques, scientists provided a more comprehensive method of analysis. We will describe a MATLAB routine written to render each of these data sets individually and/or within the same coordinate system. This approach is shown in the analysis of two samples: an integrated circuit surface mounted resistor and a machined piece of polystyrene foam. The samples chosen provide an opportunity to compare and contrast the two X‐ray techniques, identify their weaknesses and show how they are used in a complementary fashion. Copyright © 2010 John Wiley & Sons, Ltd.     

Measurement of L subshell fluorescence yield ratios of some high Z elements by selective excitation method

The L₁, L₂ and L₃ subshells of Hf, Ta and Re atoms have been excited selectively by using microprobe XRF beam line, Indus‐2, RRCAT, India. The consequent characteristic L X‐ray photons, emitted from the targets due to creations of vacancies in L subshells, are measured using silicon drift detector (X‐123) spectrometer. As the energy of synchrotron radiation increases, the contribution of characteristic L X‐ray intensity increases. The advantage of the increase in the intensity of the characteristic L X‐ray photons with an increase in the energy of synchrotron radiation has been used to determine the L subshell fluorescence yield ratios of Hf, Ta and Re atoms by adopting the selective excitation method. The measured ratios of L subshell fluorescence yield have been compared with theoretical and other experimental values.     

Quantitative or semi‐quantitative?–laboratory‐based WD‐XRF versus portable ED‐XRF spectrometer: results obtained from measurements on nickel‐base alloys

‘Semi‐quantitative’ analytical procedures are becoming more and more popular. Using such procedures, the question of the accuracy of results arises. The accuracy of an analytical procedure depends to a great extent on spectral resolution, counting statistics and matrix correction. Two ‘semi‐quantitative’ procedures are compared with a quantitative analytical program. Using a laboratory‐based wavelength‐dispersive x‐ray fluorescence (WD‐XRF) spectrometer and a portable energy‐dispersive x‐ray fluorescence (ED‐XRF) spectrometer, 28 different nickel‐base alloy Certified Reference Materials (CRMs) were analyzed. Line interferences and inaccurate matrix correction are reasons for deviations from the reference value. As the comparison shows, ‘semi‐quantitative’ analyses on the WD‐XRF spectrometer can be accepted as quantitative determinations. The investigations show that the results obtained with the portable ED‐XRF spectrometer do not meet the quality requirements of laboratory analysis, but they are good enough for field investigations. Copyright © 2004 John Wiley & Sons, Ltd.     

A three‐crystal spectrometer for high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy and X‐ray emission spectroscopy at SSRF

A Johann‐type spectrometer for the study of high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy, X‐ray emission spectroscopy and resonant inelastic X‐ray scattering has been developed at BL14W1 X‐ray absorption fine structure spectroscopy beamline of Shanghai Synchrotron Radiation Facility. The spectrometer consists of three crystal analyzers mounted on a vertical motion stage. The instrument is scanned vertically and covers the Bragg angle range of 71.5–88°. The energy resolution of the spectrometer ranges from sub‐eV to a few eV. The spectrometer has a solid angle of about 1.87 × 0^?3 of 4π sr, and the overall photons acquired by the detector could be 10⁵ counts per second for the standard sample. The performances of the spectrometer are illustrated by the three experiments that are difficult to perform with the conventional absorption or emission spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.     

Development of a high‐resolution confocal micro‐XRF instrument equipped with a vacuum chamber

A confocal micro‐X‐ray fluorescence (micro‐XRF) instrument equipped with a vacuum chamber was newly developed. The instrument is operated under a vacuum condition to reduce the absorption of XRF in the atmosphere. Thin metal layers were developed to evaluate the confocal volume, corresponding to depth resolution. A set of thin metal layers (Al, Ti, Cr, Fe, Ni, Cu, Zr, Mo, and Au) was prepared by a magnetron sputtering technique. The depth resolutions of the new instrument were varied from 56.0 to 10.9 µm for an energy range from 1.4 to 17.4 keV, respectively. The lower limit of detection (LLD) was estimated by comparison with a glass standard reference material NIST SRM 621). The LLDs obtained by a conventional micro‐XRF were compared with the LLDs obtained by a confocal micro‐XRF instrument. The LLDs were improved in the measurement under confocal configuration because of the reduction of background intensity. Finally, layered materials related to forensic investigation were measured. The confocal micro‐XRF instrument was able to nondestructively obtain the distribution of light elements that cannot be detected by measurement in air. Copyright © 2013 John Wiley & Sons, Ltd.     

XRF analysis without sampling of Etruscan depurata pottery for provenance classification

In order to settle the provenance of a set of ancient ceramic shards, the elemental composition data acquired are usually treated by multivariate analysis techniques. The quantitative X‐ray fluorescence (XRF) analysis is an appropriate tool if it is possible to grind ceramics and analyze a sample that is representative of the object. If we deal particularly with well‐preserved objects, we are often not allowed to sample them. Moreover, moving these objects from museum could be unfeasible as well. The aim of this work is to evaluate if spot XRF analysis on integral objects is adequate to classify row clay provenance even if ceramics is not an intrinsically homogeneous material. So, we performed measurements on a set of Etruscan fine ware already classified according to the archaeological, chemical and mineralogical examination. For each sample, several measurement points in polished areas were considered for XRF analyses, allowing a correct provenance classification. Copyright © 2010 John Wiley & Sons, Ltd.     

A device for X‐Ray elemental mapping using annular radioisotope source

An energy‐dispersive system is described for elemental mapping by X‐ray fluorescence spectrometry. The present study describes the design of an X‐ray fluorescence spectrometer and presents its performance in elemental mapping applications. The spectrometer is based on a new ring‐shaped collimator with a pinhole in the center of it and a ring‐shaped Am‐241 isotope mounted in the collimator as a source for excitation of X‐ray fluorescence. The photons were detected by high‐resolution Si (Li) detector coupled to a multi‐channel analyser and cooled by liquid nitrogen. In this study, we used two samples; one of them was made from pure elemental powders, and the second one was a piece of a stone and three types of maps were plotted. In the maps type one, the areas of the elements were shown with a single color. These maps only show the location of the elements in the sample. In the maps type two, the area of each element was shown with different colors because of the count (intensity) related to the area. In the third type of the maps for each element, depending on the elements' position on the sample, the counts were plotted in three dimensions. The areas with higher intensity have greater height, and areas with lower intensity have lower altitude. These two last types of maps provide information about the homogeneity or heterogeneity of the elemental distribution in the samples. The spectrometer can perform non‐destructive analyses of samples and objects in the air. Copyright © 2017 John Wiley & Sons, Ltd.     

Microfluidic sample preparation for elemental analysis in liquid samples using micro X‐ray fluorescence spectrometry

The integration of microfluidic devices with micro X‐ray fluorescence (micro‐XRF) spectrometry offers a new approach for the direct characterization of liquid materials. A sample presentation method based on use of small volumes (<5 µl) of liquid contained in an XRF‐compatible device has been developed. In this feasibility study, a prototype chip was constructed, and its suitability for XRF analysis of liquids was evaluated, along with that of a commercially produced microfluidic device. Each of the chips had an analytical chamber which contained approximately 1 µl of sample when the device was filled using a pipette. The performance of the chips was assessed using micro‐XRF and high resolution monochromatic wavelength dispersive X‐ray fluorescence, a method that provides highly selective and sensitive detection of actinides. The intended application of the device developed in this study is for measurement of Pu in spent nuclear fuel. Aqueous solutions and a synthetic spent fuel matrix were used to evaluate the devices. Sr, which has its Kα line energy close to the Pu Lα line at 14.2 keV, was utilized as a surrogate for Pu because of reduced handling risks. Between and within chip repeatability were studied, along with linearity of response and accuracy. The limit of detection for Sr determination in the chip is estimated at 5 ng/µl (ppm). This work demonstrates the applicability of microfluidic sample preparation to liquid characterization by XRF, and provides a basis for further development of this approach for elemental analysis within a range of sample types. Copyright © 2014 John Wiley & Sons, Ltd.     

Implementation of a beam deflection system for studies of liquid interfaces on beamline I07 at Diamond

X‐ray optics, based on a double‐crystal deflection scheme, that enable reflectivity measurements from liquid surfaces/interfaces have been designed, built and commissioned on beamline I07 at Diamond Light Source. This system is able to deflect the beam onto a fixed sample position located at the centre of a five‐circle diffractometer. Thus the incident angle can be easily varied without moving the sample, and the reflected beam is tracked either by a moving Pilatus 100K detector mounted on the diffractometer arm or by a stationary Pilatus 2M detector positioned appropriately for small‐angle scattering. Thus the system can easily combine measurements of the reflectivity from liquid interfaces (Q_z > 1 Å^?1) with off‐specular data collection, both in the form of grazing‐incidence small‐angle X‐ray scattering (GISAXS) or wider‐angle grazing‐incidence X‐ray diffraction (GIXD). The device allows operation over the energy range 10–28 keV.     

X‐ray tube spectral measurement method for quantitative analysis of X‐ray fluorescence analysis

Lα and Lβ X‐ray fluorescence spectra of a lead metallic sheet were measured using an energy dispersive X‐ray spectrometer by changing the X‐ray tube voltage and the material of the primary filter. The Lα to Lβ intensity ratio changed from Lα: Lβ = 3: 1 at 15 kV to Lα: Lβ = 1: 1 at 50 kV depending on the X‐ray tube voltage and the filter. The scattered X‐ray spectra of an acrylic slab instead of the sample in the sample holder were measured by changing the applied voltage and the material of the primary filter. The calculated values of the Pb Lα/Lβ intensity ratio of the metallic sheet using the Shiraiwa–Fujino formula by inserting the scattered X‐ray spectra of an acrylic plate as incident X‐ray spectra and the fundamental parameters taken from the Elam database were in good agreement with the experimental ones. We conclude that we can obtain an incident X‐ray spectrum approximately by measuring the scattered X‐ray spectrum without measuring the direct incident beam. Copyright © 2010 John Wiley & Sons, Ltd.     

ED‐XRF set‐up for size‐segregated aerosol samples analysis

The knowledge of size‐segregated elemental concentrations in atmospheric particulate matter (PM) gives a useful contribution to the complete chemical characterisation; this information can be obtained by sampling with multi‐stage cascade impactors. In this work, samples were collected using a low‐pressure 12‐stage Small Deposit Impactor and a 13‐stage rotating Micro Orifice Uniform Deposit Impactor^?. Both impactors collect the aerosol in an inhomogeneous geometry, which needs a special set‐up for X‐ray analysis. This work aims at setting up an energy dispersive X‐ray fluorescence (ED‐XRF) spectrometer to analyse quantitatively size‐segregated samples obtained by these impactors. The analysis of cascade impactor samples by ED‐XRF is not customary; therefore, as additional consistency test some samples were analysed also by particle‐induced X‐ray emission (PIXE), which is more frequently applied to size‐segregated samples characterised by small PM quantities. A very good agreement between ED‐XRF and PIXE results was obtained for all the detected elements in samples collected with both impactors. The good inter‐comparability proves that our methodology is reliable for analysing size‐segregated samples by ED‐XRF technique. The advantage of this approach is that ED‐XRF is cheaper, easier to use, and more widespread than PIXE, thus promoting an intensive use of multi‐stage impactors. Copyright © 2011 John Wiley & Sons, Ltd.     

A new portable XRF spectrometer with beam stability control

A new portable XRF spectrometer which allows control of the energy and the intensity stability of the emitted x‐ray beam has been designed and built. The control is obtained by measuring the x‐ray fluorescence generated by a double Ag/Ba thin target when crossed by the x‐ray beam during a measurement. The silver and barium fluorescence K lines are detected by an ancillary Si‐PIN detector and analysed by software developed at the LNS/INFN laboratories. The new portable spectrometer, the beam stability control method, the evaluation of the system and some quantitative applications of interest in the cultural heritage field are presented and discussed. Copyright © 2004 John Wiley & Sons, Ltd.