Elemental depth profile of faux bamboo paint in Forbidden City studied by synchrotron radiation confocal µ‐XRF

A three‐dimensional (3D) analysis of micro x‐ray fluorescence (XRF), namely confocal µ‐XRF, has been constructed at 4W1B beamline of the Beijing synchrotron radiation facility (BSRF). A KB mirror is applied to focus the incident beam and a polycapillary half‐lens in front of the Si(Li) detector is used to limit the visual field of the detector. The faux bamboo paint in Emperor Qianlong's Lodge of Retirement in Forbidden City was analyzed nondestructively by this method. A stratified structure in the paint is disclosed and the results show that the painting was probably restored once in the past, following the same painting technique as originally used. Copyright © 2008 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.     

利用毛细管X光透镜共聚焦微束X射线荧光技术对单根头发中元素空间分布进行无损扫描分析

头发中的元素与人的饮食和健康状况有关,对头发中元素的分析,不仅可用于刑事物证鉴别,还可为疾病的预防和治疗提供依据,因此,如何检测头发中元素分布等信息倍受人们关注。本文利用基于毛细管X光透镜和实验室普通X射线光源的共聚焦微束X射线荧光技术对单根头进行了无损扫描分析,分析了单根头发中元素的空间分布。在该毛细管X光透镜共聚焦微束X射线荧光技术中,毛细管X光会聚透镜的出口焦斑和毛细管X光平行束透镜的入口焦斑处在共聚焦状态,从而形成共聚焦微元,探测器只能探测到来自该共聚焦微元中的X射线信号,降低了背底信号对X射线荧光谱的影响,从而有利于提高该共聚焦X射线荧光技术的分析精度。该共聚焦技术中采用了具有高功率密度增益的毛细管X光会聚透镜,降低了该共聚焦X射线荧光技术对X射线光源功率的要求,从而保证了该共聚焦技术可以采用实验室普通X射线光源,降低了实验成本。实验表明,毛细管X光透镜共聚焦微束X射线荧光技术在单根头发元素分布检测中具有应用价值。     

Confocal macro X‐ray fluorescence spectrometer on commercial 3D printer

Novel confocal X‐ray fluorescence (XRF) spectrometer was designed and constructed for 3D analysis of elementary composition in the surface layer of spatially extended objects having unlimited chemical composition and geometrical shape. The main elements of the XRF device were mounted on a moving frame of a commercial 3D printer. The XRF unit consists of a silicon drift detector and a low‐power transmission‐type X‐ray tube. Both the excitation and secondary X‐ray beams were formed and regulated by simple collimator systems in order to create a macro confocal measuring setup. The spatial accuracy of the mechanical stages of the 3D printer achieved was less than 5 μm at 100‐μm step‐size. The diameter of the focal spot of the confocal measuring arrangement was between 1.5 and 2.0 mm. The alignment of the excitation and secondary X‐ray beams and the selection of the measuring spot on the sample surface were ensured by two laser beams and a digital microscope for visualization of the irradiated spot. The elements of the optical system together with the XRF spectrometer were mounted on the horizontal arm of the 3D printer, which mechanical design is capable of synchronized moving the full spectroscopic device within vertical directions. Analytical capability and the 3D spatial resolution of the confocal spectrometer were determined. Copyright © 2017 John Wiley & Sons, Ltd.     

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.     

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.     

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。     

Confocal three-dimensional micro-X-ray fluorescence spectroscopy used to retrieve the information covered in printed paper

Confocal three-dimensional micro-X-ray fluorescence (3D-μXRF) spectroscopy based on laboratory X-ray tube was employed to unravel the three-dimensional (3D) distribution of metal element (Fe) inner the paper. According the distribution of the Fe in the paper, the information covered in the printed paper could be retrieved. Before the experiment, the performance of the confocal 3D-μXRF setup was described. The two-dimensional (2D) mapping of printed character covered by the opaque tape and contaminated by the black ink was scanned by confocal 3D-μXRF setup. Furthermore, 2D and 3D mapping of a printed number covered by the paper with printed character was performed by micro-X-ray fluorescence and confocal 3D-μXRF setup, respectively. The scanning results indicated that confocal 3D-μXRF was more suitable for retrieving the information covered in the paper. Furthermore, the confocal 3D-μXRF setup has potential application on the identification of unseen letter or painting that was covered by others, such as ink.     

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 critical analysis of the application of EDXRF spectrometry on complex stratigraphies

In this work, the potentialities and limits of the investigation by portable energy‐dispersive X‐ray fluorescence (XRF) of complex polychrome stratigraphies are discussed. Data are affected by the mutual influence effects of the chemical elements that characterize mineral pigments, by the sequence and the thickness of the paint layers in the stratigraphies and by the size of pigment grains. Sequences of pictorial layers, which produce the typical stratigraphy of cold‐painted terracotta and wooden sculptures, have been prepared and then analysed by means of two portable X‐ray spectrometers: Innov X Systems Alpha 4000 (Tantalum X‐ray tube, 40 kV and 7 µA) and Assing Lithos 3000 (Molybdenum X‐ray tube, 25 kV and 300 µA). For each layer of pigment, the XRF spectrum was acquired and the areas of K and L peaks of characterizing elements were calculated. Moreover, the thickness of the layers was determined using XRF data following an algorithm already shown and the values have been compared with those measured on polished cross sections observed by optical microscope in reflected light. Copyright © 2011 John Wiley & Sons, Ltd.     

Certification of NIST SRM 2569 Lead Paint Films for Children's Products

SRM 2569 Lead Paint Films for Children's Products is a new Standard Reference Material (SRM) developed for use primarily with X‐ray fluorescence spectrometry (XRF) instrumentation. It consists of three paint coatings, with nominally 0, 90, and 300 mg/kg of Pb added, on polyester substrates. The levels of Pb are appropriate for use when validating test methods intended for testing product compliance with the Consumer Product Safety Improvement Act. The Pb mass fraction, mass Pb per unit area, paint density, and paint thickness are all characterized to make these materials useful to users of different XRF instrumentation. These parameters are consistent with one another and can be used to demonstrate mathematical conversions between units of mass fraction and mass per unit area. The assigned values for these parameters were obtained through direct determinations using instrumental methods and via calculations using measured values for paint ingredients, paint composition, and physical properties. The paints are highly homogeneous among units, although within units, some localized areas enriched in Pb can be observed using microbeam XRF instrumentation. For this reason, SRM 2569 is not recommended for use with measured areas smaller than 1 mm diameter. The development of SRM 2569 is a good case study for the use of multiple, interrelated parameters and test methods to demonstrate the comparability of values derived from a variety of measurement processes. Published 2012. This article is a US Government work and is in the public domain in the USA.     

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.     

A non invasive method to detect stratigraphy, thicknesses and pigment concentration of pictorial multilayers based on EDXRF and vis-RS: in situ applications

Energy dispersive XRF analysis (EDXRF) in association with visible reflectance spectroscopy (vis-RS), both achieved by portable instruments, can be successfully applied, in a wide range of cases, to investigate wood or canvas paintings in order to obtain some stratigraphic information with non-invasive techniques. The specific aim of this work is to use them as quantitative tools: EDXRF to reconstruct the thicknesses of the detected layers, vis-RS to report pigment concentration in the uppermost layer. The method has been tested in the laboratory on paint layers with different composition of about 50 multilayers and more than 100 single layers [12]. We present here some in situ analyses of famous paintings by Andrea Mantegna and Giovanni Bellini, compared with stratigraphic optical microscopy observations on cross sections. Advantages and limits are pointed out. PACS  78.40.-q; 78.30.-j; 78.70.En     

A deep view in cultural heritage—confocal micro X-ray spectroscopy for depth resolved elemental analysis

Quantitative X-ray fluorescence (XRF) and particle induced X-ray emission (PIXE) techniques have been developed mostly for the elemental analysis of homogeneous bulk or very simple layered materials. Further on, the microprobe version of both techniques is applied for 2D elemental mapping of surface heterogeneities. At typical XRF/PIXE fixed geometries and exciting energies (15–25 keV and 2–3 MeV, respectively), the analytical signal (characteristic X-ray radiation) emanates from a variable but rather extended depth within the analyzed material, according to the exciting probe energy, set-up geometry, specimen matrix composition and analyte. Consequently, the in-depth resolution offered by XRF and PIXE techniques is rather limited for the characterization of materials with micrometer-scale stratigraphy or 3D heterogeneous structures. This difficulty has been over-passed to some extent in the case of an X-ray or charged particle microprobe by creating the so-called confocal geometry. The field of view of the X-ray spectrometer is spatially restricted by a polycapillary X-ray lens within a sensitive microvolume formed by the two inter-sectioned focal regions. The precise scanning of the analyzed specimen through the confocal microvolume results in depth-sensitive measurements, whereas the additional 2D scanning microprobe possibilities render to element-specific 3D spatial resolution (3D micro-XRF and 3D micro-PIXE). These developments have contributed since 2003 to a variety of fields of applications in environmental, material and life sciences. In contrast to other elemental imaging methods, no size restriction of the objects investigated and the non-destructive character of analysis have been found indispensable for cultural heritage (CH) related applications. The review presents a summary of the experimental set-up developments at synchrotron radiation beamlines, particle accelerators and desktop spectrometers that have driven methodological developments and applications of confocal X-ray microscopy including depth profiling speciation studies by means of confocal X-ray absorption near edge structure (XANES) spectroscopy. The solid mathematical formulation developed for the quantitative in-depth elemental analysis of stratified materials is exemplified and depth profile reconstruction techniques are discussed. Selected CH applications related to the characterization of painted layers from paintings and decorated artifacts (enamels, glasses and ceramics), but also from the study of corrosion and patina layers in glass and metals, respectively, are presented. The analytical capabilities, limitations and future perspectives of the two variants of the confocal micro X-ray spectroscopy, 3D micro-XRF and 3D micro-PIXE, with respect to CH applications are critically assessed and discussed.     

Methodological challenges of optical tweezers‐based X‐ray fluorescence imaging of biological model organisms at synchrotron facilities

Recently, a radically new synchrotron radiation‐based elemental imaging approach for the analysis of biological model organisms and single cells in their natural in vivo state was introduced. The methodology combines optical tweezers (OT) technology for non‐contact laser‐based sample manipulation with synchrotron radiation confocal X‐ray fluorescence (XRF) microimaging for the first time at ESRF‐ID13. The optical manipulation possibilities and limitations of biological model organisms, the OT setup developments for XRF imaging and the confocal XRF‐related challenges are reported. In general, the applicability of the OT‐based setup is extended with the aim of introducing the OT XRF methodology in all research fields where highly sensitive in vivo multi‐elemental analysis is of relevance at the (sub)micrometre spatial resolution level.     

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.     

Shades of green in 15th century paintings: combined microanalysis of the materials using synchrotron radiation XRD, FTIR and XRF

A representative selection of green paintings from fifteenth century Catalonia and the Crown of Aragon are analyzed by a combination of synchrotron radiation microanalytical techniques including FTIR, XRD, and XRF. The green pigments themselves are found to be a mixture of copper acetates/basic copper acetates and basic copper chlorides. Nevertheless, a broader range of green shades were obtained by mixing the green pigment with yellow, white, and blue pigments and applied forming a sequence of micrometric layers. Besides the nature of the pigments themselves, degradation and reaction products, such as carboxylates, formates and oxalates were also identified. Some of the copper based compounds, such as the basic copper chloride, may be either part of the original pigment or a weathering product. The high resolution, high brilliance, and small footprint of synchrotron radiation proved to be essential for the analysis of those submillimetric paint layers made of a large variety of compounds heterogeneous in nature and distribution and present in extremely low concentrations.     

Characterization and performance of the femtosecond fluorescence up-conversion microscope

The characterization and performance of the femtosecond fluorescence up-conversion microscope is reported in this paper. This new fluorescence microscope is a combination of the frequency up-conversion technique and a confocal optical configuration, which simultaneously achieves femtosecond time and nanometer space resolution. The femtosecond time resolution was evaluated by measuring the rise up of time-resolved fluorescence from a dye molecule, and it was 520 fs and 460 fs with 100× (N.A.=1.3) and 40× (N.A.=0.75) objective lenses, respectively. The best transverse (XY) resolution was 0.34 m with the 100× objective lens for 400 nm excitation. An axial (Z) resolution as high as 1.1 m was obtained for 600 nm fluorescence detection with a 50 m pinhole and a 100× objective lens. The axial resolution was remarkably improved compared with ordinary confocal microscopes owing to the up-conversion process, which requires spatial overlap between the tightly focused gate and the fluorescence beams. Femtosecond time-resolved fluorescence measurements were performed for micro-meter sized particles in liquids, fluorescent beads and C519/toluene micro droplets, by using the laser trapping technique. The high potential of the fluorescence up-conversion microscope was demonstrated. PACS 78.47.+p; 87.64.-t; 82.53.-k     

Spectroscopic Application of Realgar Using X-ray Fluorescence and Raman Spectroscopy

ABSTRACT

Samples of realgar ore were collected from the hydrothermal products of the Eocene volcanic material of the Erzurum region in Turkey. The prepared samples were analyzed by polarized energy dispersive X-ray fluorescence (PEDXRF) and by confocal Raman spectroscopy (CRS). The goal of this study was to figure out the chemical composition of realgar and its properties through PEDXRF and CRS and the optical characteristic features under the polarized microscope. The result of the XRF analysis shows the collected realgar samples are mainly composed of As, S, Si, and Mg in different proportions. The contents of As in realgar change from 36.55% through 31.49% to 5.97% in the analyzed samples. The strong peak of the realgar samples is at 352 cm^?1, and a weaker peak exists around 190 cm^?1. The accuracy and precision of the technique for chemical analysis is demonstrated by analyzing CRM 2126-81. The realgar ores were studied by use of CRS and polarized microscopy.