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1.
This paper carries the results of an evaluation of various materials, which may be used to aid in the release of a fused bead from its mould during a wavelength‐dispersive x‐ray fluorescence (WD‐XRF) measurement. The following bead‐releasing agents were studied: NaI, LiBr, NH4I, and LiI. Each was incorporated in different quantities, as a solid and/or in an aqueous solution, together with a flux, into samples of ceramic raw materials. Release agent interference in the WD‐XRF measurement was analysed, and the optimum quantity of release agent needed to obtain suitable beads for WD‐XRF measurement was determined. The best results were obtained for LiI, which yielded reproducible beads without significant interference in the WD‐XRF measurement when a relatively small quantity (0.11 LiI g/bead) was used. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

2.
This study was performed to develop a method for directly controlling the chemical composition of clay slurries used in preparing ceramic floor and wall tile bodies by wavelength‐dispersive X‐ray fluorescence (WD‐XRF) spectrometry, without the prior need to dry and prepare the samples as fused beads or pellets for WD‐XRF measurement, owing to the importance of knowing the suspension chemical composition in real time for appropriate control of the industrial process. The study was conducted on a wide range of ceramic floor and wall tile bodies, which are used to prepare different suspensions. The influence of suspension viscosity (from 300 to 7000 cp), of suspension solids content (between 66 and 69%), and of the type of body composition (floor or wall tile) on the WD‐XRF measurement was determined. In these viscosity and solid content ranges, no appreciable differences were observed in the WD‐XRF measurement results, indicating that the possibly arising variations in viscosity and solids content in such clay suspensions in industrial practice do not influence the WD‐XRF measurement. In contrast, the type of body composition did influence the WD‐XRF measurement. The developed method is rapid, reproducible, and accurate, which was verified by analysis of the materials using the customary method of WD‐XRF measurement on fused beads. In addition, this method is cheaper and more harmless to the environment; it minimises waste generation, since no sample preparation is required and the plastic sample holders can be reused, thanks to the reusable sample holder system designed at the Instituto de Tecnología Cerámica laboratories. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

3.
This article describes the details of metal concentrations evaluated using wavelength dispersive X‐ray fluorescence (WD‐XRF) spectrometry. A total of 22 elements, Na, Mg, Al, Si, P, S, K, Ti, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb, Ba, Au, and Sn from 16 Ayurvedic medicines were characterized. The method was validated by analyzing the six certified reference materials of soil standards [NIST SRM‐2710, CRM 027‐050 (US‐EPA certified), PS‐1, TILL‐1 and TILL‐4 (Canadian certified reference material, CCRMP) and JSO‐1 (Japanese certified reference material)]. The elemental concentrations in all the standards are found to be within ± 10% of the reported values. Crystalline phases in the individual drug samples were explained by powder X‐ray diffraction (XRD) technique. Qualitative phase identification was done using the ICDD database. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

4.
《X射线光谱测定》2003,32(2):129-138
A risk assessment study of the air quality in the surrounding of roads covered with slags coming from the non‐ferrous metal industry was performed. A monitoring campaign was carried out at three locations in Flanders by collecting the PM10 fraction and the total suspended particulates (TSP) of the airborne dust particles, entrapping heavy metals, on membrane filters. The heavy metal concentration on the dust filters was determined by wavelength‐dispersive x‐ray fluorescence (WD‐XRF) spectrometry. The XRF calibration curves were set up with filter standards prepared in the laboratory using an aerosol‐generated loading system. The acquired WD‐XRF results were confirmed by inductively coupled plasma atomic emission spectrometric (ICP‐AES) measurements after acid digestion on a selected number of filters. Electron probe microanalysis (EPMA) confirmed that aerosol‐loaded filter standards and dust filters with a concentration level of the analyzed element below 3300 ng cm?2 were homogeneously distributed. Dust filters with higher concentrations, and especially filters loaded with the TSP fraction, reflected an inhomogeneous distribution of the analyzed element on the filter. The WD‐XRF analytical results acquired in the monitoring campaign revealed that the concentration of Pb on the dust filters never exceeded the immission standard (yearly average) of 2000 ng m?3. It can be stated that the impact on human health is limited and can still be reduced by covering the polluted roads with a layer of asphalt. Further evaluation of soil and water samples from the nearby surroundings reveals that the heavy metal content in the slags makes an important contribution to environmental pollution, especially the contamination of groundwater. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

5.
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.  相似文献   

6.
《X射线光谱测定》2003,32(4):285-298
The experimental values of L x‐ray fluorescence (XRF) cross‐sections are not available for all the elements in the range La–U, at all the photon energies E in the range EL1 ≤ EEK. To generate L XRF cross‐sections, where experimental measurements are not available, two empirical relations have been developed, one between the L XRF cross‐sections and photon energy and the other between the L XRF cross‐sections and atomic number. For the measured data on L XRF cross‐sections at incident energies between Ll and K edges of an element and the data on L XRF cross‐sections for elements in the range 57 ≤ Z ≤ 92 at an energy value, polynomial fits have been derived. The L XRF cross‐section values generated with the derived empirical relations were found to be in agreement with the experimental values within their experimental uncertainties. Subsequently, a software code IGELCS was developed to interpolate and to generate the cross‐sections at inter‐energies and for inter‐elements in a single computer run. The running of the software requires minimum input data on five elements at five common energies. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

7.
In vivo time‐resolved Cr and Ca X‐ray fluorescence (XRF) mapping measurements were performed in a laboratory over a period of 69 days on a living common aquatic plant Egeria densa that was immersed in 5 mM K2CrO4 aqueous solution. The time and spatial resolution for each time‐resolved XRF map were ~1.6 days and 1 × 1 mm2, respectively. The obtained XRF maps exhibited characteristic localized Cr and Ca areas where the XRF signals were especially strong (‘hot spots’), and this indicated the necessity of preliminary millimeter‐resolution surveying in XRF microscopy. Ca hot spots were detected prior to Cr(VI) immersion and nearly disappeared after immersion in deionized water for 2 weeks and the Cr(VI) solution for 1 week. After these immersions, a Cr hot spot was formed at approximately the same location of the missing Ca hot spot, which suggests that the original Ca‐accumulated regions were substituted for the isolation of Cr species when they were introduced. The sizes and intensity distributions of the Cr hot spots were sensitive to the Cr(VI) exposure approximately 1 week prior to each XRF measurement. This sensitivity suggests potential applications of E. densa as a Cr(VI) biomonitor in aquatic environments. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

8.
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.  相似文献   

9.
Double-pulse LIBS and ED XRF usabilities for quantitative analysis of Ti in samples of cotton, wool, and viscose fabrics were compared to each other. The analyzed samples were prepared by stippling a particular fabric with TiO2 nanoparticle sol (particle size 100 nm). Both spectrometers were calibrated with the aid of the same sets of authentic fabric samples previously analyzed by ICP OES after the microwave digestion. Average values of the Ti concentration calculated from five repeated measurements of the same sample obtained by LIBS and ED XRF were comparable for all types of the tested materials (100∙(CTi-LIBS/CTi-ED XRF)) ≅ 96–109%), but the precision of analysis expressed as RSD (relative standard deviation) was usually better for ED XRF (RSDLIBS from 9 to 25%, RSDED XRF from 3 to 17%). Poor RSD values of LIBS measurements were observed mainly in the case of samples with lower areal weights. Limits of detection calculated as a triple standard deviation of five repeated measurements of Ti in a sample with the low concentration of the analyte were comparable for both methods (LODLIBS = from 15 to 97, and LODED XRF = from 21 to 64, all in mg/kg).  相似文献   

10.
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  相似文献   

11.
Quantum transport in a single‐molecule contact made of a prismane cluster C8 attached to quasi‐one‐dimensional gold (100) electrodes is calculated using the ab initio methodology based on the density‐functional theory and the nonequilibrium Green's functions formalism. Varying the junction length L we calculate the length dependence of the zero‐bias conductance G (L) and, for a set of the interelectrode distances, the current–voltage (IV) characteristics. It is shown that the G (L) dependence is strongly nonmonotonic with a sharp dip at some value of L. With increase in L, the IV curves change their shape from monotonic curves to curves with a negative differential resistance area and, for a larger L, the junction exhibits the super‐insulating state, i.e., within some applied bias voltage range the current through the junctions is about two orders of magnitude less than the current outside this bias range. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   

12.
Kidney stone is the most painful and prevalent urological disorder of the urinary system throughout the world. Thus, analysis of kidney stones is an integral part in the evaluation of patents having stone disease. Spectroscopic investigations of stones provide an idea about the pathogenesis of stones for its better cure and treatment. Hence, the present work targets multispectroscopic investigations on kidney stones using Fourier transform infrared (FTIR) and wave dispersive X‐ray fluorescence (WD‐XRF) spectroscopy which are the most useful analytical methods for the purpose of bio‐medical diagnostics. In the present study, FTIR spectral method is used to investigate the chemical composition and classification of kidney stones. The multicomponents of kidney stones such as calcium oxalate, hydroxyl apatite, phosphates, carbonates, and struvite were investigated and studied. Qualitative and quantitative determination of major and trace elements present in the kidney stones was performed employing WD‐XRF spectroscopy. The wide range of elements determined in the kidney stones were calcium (Ca), magnesium (Mg), phosphorous (P), sodium (Na), potassium (K), chlorine (Cl), sulfur (S), silicon (Si), iodine (I), titanium (Ti), iron (Fe), ruthenium (Ru), zinc (Zn), aluminum (Al), strontium (Sr), nickel (Ni), copper (Cu), and bromine (Br). For the first time, ruthenium was detected in kidney stone samples employing WD‐XRF in very low concentration. Our results revealed that the presence and relative concentrations of trace elements in different kinds of stones are different and depend on the stone types. From the experiments carried out on kidney stones for trace elemental detection, it was found that WD‐XRF is a robust analytical tool that can be useful for the diagnosis of urological disorders. We have also compared our findings with the results reported using XRF technique. The results obtained in the present paper show interesting prospects for FTIR and WD‐XRF spectrometry in nephrolithiasis. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

13.
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.  相似文献   

14.
The X‐ray mass attenuation coefficients of silver were measured in the energy range 5–20 keV with an accuracy of 0.01–0.2% on a relative scale down to 5.3 keV, and of 0.09–1.22% on an absolute scale to 5.0 keV. This analysis confirms that with careful choice of foil thickness and careful correction for systematics, especially including harmonic contents at lower energies, the X‐ray attenuation of high‐Z elements can be measured with high accuracy even at low X‐ray energies (<6 keV). This is the first high‐accuracy measurement of X‐ray mass attenuation coefficients of silver in the low energy range, indicating the possibility of obtaining high‐accuracy X‐ray absorption fine structure down to the L1 edge (3.8 keV) of silver. Comparison of results reported here with an earlier data set optimized for higher energies confirms accuracy to within one standard error of each data set collected and analysed using the principles of the X‐ray extended‐range technique (XERT). Comparison with theory shows a slow divergence towards lower energies in this region away from absorption edges. The methodology developed can be used for the XAFS analysis of compounds and solutions to investigate structural features, bonding and coordination chemistry.  相似文献   

15.
A method for the quantitative analysis of Co, Ni, Pd, Ag, and Au in the scrapped printed‐circuit‐board ash by X‐ray fluorescence (XRF) spectrometry using loose powder was developed. The printed‐circuit‐board samples were converted to ash pyrolytically in porcelain crucibles by sequential heating using a gas burner and electric furnace, and then were ground with a ball mill. The calibrating standards were prepared by adding the appropriate amounts of NiO powder and aqueous standard solutions containing Co, Pd, Ag, and Au to the base mixtures of Al2O3 (5.0 mass%), SiO2 (49 mass%), CaCO3 (11 mass%), Fe2O3 (3.3 mass%), and CuO (30 mass%) as a matrix. Then, 10 g of the resulting mixtures were dried and homogenized for 90 min with a V‐type mixing machine. Specimens for XRF analysis were prepared from the so‐called loose‐powder method in which powder samples were compacted into a hole (12.0‐mm diameter and 5.0‐mm height) in an acrylic plate and covered with a 6‐µm thickness of polypropylene film. Matrix effects were corrected using the intensity value of Compton scattering for PdKα, AgKα, and AuLβ2, and that of background scattering at 35.8° (2θ) for CoKα and NiKα. The detection limits corresponding to three times the standard deviation of the blank intensity were 2.5–45 µg g?1. The proposed method was validated against the pressed‐powder‐pellet method by comparing the calibration curves. Moreover, the concentrations of Co, Ni, Pd, and Ag determined using the proposed XRF method were approximately the same as those resulting from an atomic‐absorption‐spectrometric analysis. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

16.
《X射线光谱测定》2004,33(4):294-300
‘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.  相似文献   

17.
The ―NH2, ―NO2, ―NHNO2, ―C(NO2)3 and ―CF(NO2)2 substitution derivatives of 4,4′,5,5′‐tetranitro‐2,2′‐1H,1′H‐2,2′‐biimidazole were studied at B3LYP/aug‐cc‐pVDZ level of density functional theory. The crystal structures were obtained by molecular mechanics (MM) methods. Detonation properties were evaluated using Kamlet–Jacobs equations based on the calculated density and heat of formation. The thermal stability of the title compounds was investigated via the energy gaps (?ELUMO ? HOMO) predicted. Results show that molecules T5 (D = 10.85 km·s?1, P = 57.94 GPa) and T6 (D = 9.22 km·s?1, P = 39.21 GPa) with zero or positive oxygen balance are excellent candidates for high energy density oxidizers (HEDOs). All of them appear to be potential explosives compared with the famous ones, octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetraazocane (HMX, D = 8.96 km·s?1, P = 35.96 GPa) and hexanitrohexaazaisowurtzitane (CL‐20, D = 9.38 km·s?1, P = 42.00 GPa). In addition, bond dissociation energy calculation indicates that T5 and T6 are also the most thermally stable ones among the title compounds. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

18.
The general matrix theory of the photoelectron/fluorescence excitation in anisotropic multilayer films at the total reflection condition of X‐rays has been developed. In a particular case the theory has been applied to explain the oscillation structure of L2,3 XANES spectra for a SiO2/Si/SiO2/c‐Si sample in the pre‐edge region which has been observed by a sample current technique at glancing angles of synchrotron radiation. Remarkably the phase of the oscillations is reversed by a ~2° angle variation. The observed spectral features are found to be a consequence of waveguide mode creation in the middle layer of strained Si, which changes the radiation field amplitude in the top SiO2 layer. The fit of the data required the correction of the optical constants for Si and SiO2 near the Si L2,3‐edges.  相似文献   

19.
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.  相似文献   

20.
Earlymost Villafranchian fossil bones of an artiodactyl and a perissodactyl from the Milia excavation site in Grevena, Greece, were studied in order to evaluate diagenetic effects. Optical microscopy revealed the different bone types (fibro‐lamellar and Haversian, respectively) of the two fragments and their good preservation state. The spatial distribution of bone apatite and soil‐originating elements was studied using micro‐X‐ray fluorescence (µ‐XRF) mapping and scanning electron microscopy. The approximate value of the Ca/P ratio was 2.2, as determined from scanning electron microscopy measurements. Bacterial boring was detected close to the periosteal region and Fe bearing oxides were found to fill bone cavities, e.g. Haversian canals and osteocyte lacunae. In the perissodactyl bone considerable amounts of Mn were detected close to cracks (the Mn/Fe weight ratio takes values up to 3.5). Goethite and pyrite were detected in both samples by means of metallographic microscopy. The local Ca/P ratio determined with µ‐XRF varied significantly in metal‐poor spots indicating spatial inhomogeneities in the ionic substitutions. XRF line scans that span the bone cross sections revealed that Fe and Mn contaminate the bones from both the periosteum and medullar cavity and aggregate around local maxima. The formation of goethite, irrespective of the local Fe concentration, was verified by the Fe K‐edge X‐ray absorption fine structure (XAFS) spectra. Finally, Sr K‐edge extended XAFS (EXAFS) revealed that Sr substitutes for Ca in bone apatite without obvious preference to the Ca1 or Ca2 unit‐cell site occupation.  相似文献   

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