A new X-ray pinhole camera for energy dispersive X-ray fluorescence imaging with high-energy and high-spatial resolution

A new X-ray pinhole camera for the Energy Dispersive X-ray Fluorescence (ED-XRF) imaging of materials with high-energy and high-spatial resolution, was designed and developed. It consists of a back-illuminated and deep depleted CCD detector (composed of 1024 × 1024 pixels with a lateral size of 13 μm) coupled to a 70 μm laser-drilled pinhole-collimator, positioned between the sample under analysis and the CCD. The X-ray pinhole camera works in a coaxial geometry allowing a wide range of magnification values.The characteristic X-ray fluorescence is induced on the samples by irradiation with an external X-ray tube working at a maximum power of 100 W (50 kV and 2 mA operating conditions).The spectroscopic capabilities of the X-ray pinhole camera were accurately investigated. Energy response and energy calibration of the CCD detector were determined by irradiating pure target-materials emitting characteristic X-rays in the energy working-domain of the system (between 3 keV and 30 keV).Measurements were performed by using a multi-frame acquisition in single-photon counting. The characteristic X-ray spectra were obtained by an automated processing of the acquired images. The energy resolution measured at the Fe–Kα line is 157 eV.The use of the X-ray pinhole camera for the 2D resolved elemental analysis was investigated by using reference-patterns of different materials and geometries. The possibility of the elemental mapping of samples up to an area of 3 × 3 cm² was demonstrated.Finally, the spatial resolution of the pinhole camera was measured by analyzing the profile function of a sharp-edge. The spatial resolution determined at the magnification values of 3.2 × and 0.8 × (used as testing values) is about 90 μm and 190 μm respectively.     

Determination of Pt,Pd and Rh in Brassica Napus using solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry

Conventional approaches for the analysis of platinum group elements (PGEs) in plant material suffer from sample digestion which results in sample dilution and therefore requires high sample intakes to maintain the sensitivity. The presented solid-sampling method avoids sample digestion while improving sensitivity when compared to digestion-based inductively coupled plasma optical emission spectrometry (ICP-OES) methods and allows the analysis of sample masses of 5 mg or less. Detection limits of 0.38 μg g^− 1, 0.14 μg g^− 1 and 0.13 μg g^− 1 were obtained for Pt, Pd and Rh, respectively using a sample intake of 5 mg. The reproducibility of the procedure ranged between 4.7% (Pd) relative standard deviation (RSD, n = 7) and 7.1% (Rh) RSD for 25 ng analytes. For quantification, aqueous standards were applied on paper filter strips and dried. Only the dried filters were introduced into the electrothermal vaporization unit. This approach successfully removed memory-effects observed during analysis of platinum which occurred only if liquid standards came into contact with the graphite material of the furnace. The presented method for overcoming the Pt-memory-effects may be of further interest for the analysis of other carbide-forming analytes as it does not require any technical modification of the graphite furnace (e.g., metal inlays, pyrolytic coating). Owing to lack of suitable certified reference materials, the proposed method was compared with conventional ICP-OES analysis of digested samples and a good agreement was obtained. As a result of the low sample consumption, it was possible to determine the spatial distribution of PGEs within a single plant. Significant differences in PGE concentrations were observed between the shoots (stem, leaves) and the roots. Pd was mainly found in the roots, whereas Pt and Rh were also found in higher concentrations in the shoots.     

Performance of a gaseous detector based energy dispersive X-ray fluorescence imaging system: Analysis of human teeth treated with dental amalgam

Energy dispersive X-ray fluorescence (EDXRF) imaging systems are of great interest in many applications of different areas, once they allow us to get images of the spatial elemental distribution in the samples. The detector system used in this study is based on a micro patterned gas detector, named Micro-Hole and Strip Plate. The full field of view system, with an active area of 28 × 28 mm² presents some important features for EDXRF imaging applications, such as a position resolution below 125 μm, an intrinsic energy resolution of about 14% full width at half maximum for 5.9 keV X-rays, and a counting rate capability of 0.5 MHz. In this work, analysis of human teeth treated by dental amalgam was performed by using the EDXRF imaging system mentioned above. The goal of the analysis is to evaluate the system capabilities in the biomedical field by measuring the drift of the major constituents of a dental amalgam, Zn and Hg, throughout the tooth structures. The elemental distribution pattern of these elements obtained during the analysis suggests diffusion of these elements from the amalgam to teeth tissues.     

Direct determination of trace rare earth elements in ancient porcelain samples with slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

A method for the direct determination of trace rare earth elements in ancient porcelain samples by slurry sampling fluorinating electrothermal vaporization inductively coupled plasma mass spectrometry was developed with the use of polytetrafluoroethylene as fluorinating reagent. It was found that Si, as a main matrix element in ancient porcelain sample, could be mostly removed at the ashing temperature of 1200 °C without considerable losses of the analytes. However, the chemical composition of ancient porcelain sample is very complicated, which makes the influences resulting from other matrix elements not be ignored. Therefore, the matrix effect of ancient porcelain sample was also investigated, and it was found that the matrix effect is obvious when the matrix concentration was larger than 0.8 g l^− 1. The study results of particle size effect indicated that when the sample particle size was less than 0.057 mm, the particle size effect is negligible. Under the optimized operation conditions, the detection limits for rare earth elements by fluorinating electrothermal vaporization inductively coupled plasma mass spectrometry were 0.7 ng g^− 1 (Eu)–33.3 ng g^− 1(Nd) with the precisions of 4.1% (Yb)–10% (La) (c = 1 μg l^− 1, n = 9). The proposed method was used to directly determine the trace rare earth elements in ancient porcelain samples produced in different dynasty (Sui, Ming and Qing), and the analytical results are satisfactory.     

Effect of electrical charging on scanning electron microscopy-energy dispersive X-ray spectroscopy analysis of insulating materials

We investigated the conditions under which we can obtain reasonable qualitative results in scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) analysis of trace elements in insulating materials using a diluted ionic liquid (EMI-CH₃COO) and changing probe current. Below 100 nA, electrical charging of insulating materials was prevented. The probe current of 10 nA was suitable for qualitative analysis because the intensities of peaks from these materials were strong enough to detect trace elements at the concentration of 0.1 wt.% in the sample without interference by sum peaks. Diluted EMI-CH₃COO can also be used for SEM-EDX quantitative analysis of insulating materials as discharging agents. In contrast, when insulating materials were electrically charged, the obtained spectra contained characteristic X-rays of the insulating materials with low energies and of materials other than the samples such as the sample stage and the collimator in the X-ray detector. This is because electrons from the electron beam were decelerated by and deflected from the insulating materials. By coating the insulating materials with the diluted EMI-CH₃COO, the deceleration and deflection of the electron beam were prevented.     

Iron,copper, zinc and bromine mapping in cirrhotic liver slices from patients with hemochromatosis studied by microscopic synchrotron radiation X-ray fluorescence analysis in continuous scanning mode

Iron (Fe) and copper (Cu) are essential metals in physiological cell metabolism. While Fe is easy to determine biochemically in histological slices, Cu and zinc (Zn) distribution is frequently critical in confirming the presence of an overload in disturbed Fe/Cu metabolism. To analyze Fe, Cu and Zn in a near histological resolution, energy dispersive microscopic synchrotron radiation X-ray fluorescence was applied.In normal liver tissue, after fixation and imbedding in paraffin, mean Fe, Cu and Zn concentrations were 152 ± 54, 20.1 ± 4.3 and 88.919.5 μg/g sample weight, respectively. No substantial, characteristic differences in their distribution were found in the two-dimensional scans. In slices from patients with hemochromatosis mean Fe, Cu and Zn concentrations were 1102 ± 539, 35.9 ± 14.6 and 27.2 ± 6.7 μg/g sample weight, respectively. Additionally, a significant decrease in phosphorus and sulphur concentrations existed. An increased Cu around cirrhotic regenerations nodules is mostly associated with a lymphocytic infiltration in this region. Analyzing concentrations of Fe in different regions of the samples show a clear negative dependency between Fe and Cu, Cu and Zn, but a positive one between Fe and Zn.Conclusion: With a focal beam size of 15 μm in diameter a resolution of the elemental distribution was achieved which is widely comparable with stained histological slices (20× light microscope). The analysis of simultaneous determined elements reveals metabolic differences between Fe, Cu and Zn in liver tissue from patients with hemochromatosis.     

Preparation of anatase phase titanium dioxide film by non-aqueous electrodeposition

The electrodeposition–annealing route to fabricating thin film of the promising photocatalyst material anatase-titanium dioxide (anatase-TiO₂) has been studied. The sample was deposited with a solution of N,N-dimethylformamide containing titanium compound by controlled-potential technique. SEM image showed the annealed sample at 600 °C for 1 h under air provided a continuous film with a thickness of ca. 350 nm. In this sample, X-ray photoelectron spectrum corresponding to the Ti 2p peak assigned to a chemical bond of TiO₂ and X-ray diffraction peaks assigned to the anatase phase were observed, respectively. Electrochemical oxidation in sodium sulfate solution on this annealed film was enhanced in the presence of UV light radiation. These results confirm the successful synthesis of photocatalytic anatase-TiO₂ film by the electrodeposition and annealing process.     

Creation,electronic properties,disorder, and melting of two-dimensional surface-state-mediated adatom superlattices

Surface-state-mediated interactions influence the spatial distribution of adatoms at surfaces. These indirect interactions are the driving force for the creation of superlattices of individual adsorbed atoms when the adatom concentration, the sample temperature, and the adatom diffusion barrier are in a subtle balance, as it has been first reported for Ce adatoms on Ag(1 1 1). The conditions for the formation of such superlattices are discussed. Specifically, the adatom concentration is shown to modify considerably the electronic structure of the Ag(1 1 1) surface. With increasing temperature the superlattice undergoes a direct transition from a two-dimensional solid to a two-dimensional liquid. Such superlattices, consisting of magnetic adatoms, may be interesting as model systems for the study of direct and indirect magnetic interactions in two dimensions.     

Solid sampling in analysis of animal organs by two-jet plasma atomic emission spectrometry

A study of high-power two-jet plasma capabilities for the direct multi-elemental analysis of animal organs was undertaken. The experimental conditions chosen allow the direct analysis of different animal organs after drying and grinding to powder (particle size 20–200 μm). It was found that evaporation efficiency of the samples depends on the particle size and thermal stability of tissues and can be improved by reduction of a carrier gas flow. Calibration samples based on graphite powder and a tenfold dilution of powdered samples with buffer (graphite powder containing 15% NaCl) were used. 5–10 mg of the sample was quite enough to get the detection limits of elements at the level of 0.1–10 μg g^? 1. A prior carbonization procedure (not ashing) makes it possible to decrease the detection limits of elements by an order of magnitude. The validation of the techniques was confirmed by the analysis of certified reference materials NIST 8414, BCR 278R and NCS ZC 81001 as well as by using different sample preparation procedures.     

Synthesis and electrical properties of (LiCo3/5Fe1/5Mn1/5)VO4 ceramics

(LiCo_3/5Fe_1/5Mn_1/5)VO₄ ceramic was synthesized via solution-based chemical method. X-ray diffraction analysis was carried out on the synthesized powder sample at room temperature, which confirms the orthorhombic structure with the lattice parameters of a = 10.3646 (20) Å, b = 3.7926 (20) Å, c = 9.2131 (20) Å. Field emission scanning electron microscopic analysis was carried out on the sintered pellet sample that indicates grains of unequal sizes (～0.1 to 2 μm) presents average grains size with polydisperse distribution on the surface of the ceramic. Complex impedance spectroscopy (CIS) technique is used for the study of electrical properties. CIS analysis identifies: (i) grain interior, grain boundary and electrode–material interface contributions to electrical response (ii) the presence of temperature dependent electrical relaxation phenomena in the ceramics. Detailed conductivity study indicates that electrical conduction in the material is a thermally activated process. The variation of A.C. conductivity with frequency at different temperatures obeys Jonscher's universal law.     

Préparation par mécanosynthèse d’apatites strontiques dopées au lanthane et au césium

Britholites have gained much interest among researchers thanks to their potential applications as matrices for the confinement of the byproducts in the nuclear industry, such as minor actinides and long-lived fission products. However, their preparation requires a high temperature of about 1400 °C. In this work, we report the preparation by mechanochemical synthesis of strontium apatites doped with lanthanum and cesium. The reactants in stoichiometric proportions were milled for different periods from 30 min to 25 h, using a planetary ball mill. The results of X-ray diffraction and infrared spectroscopy analyses showed that it is possible to obtain such apatite by a suitable grinding. However, there was formation of secondary phases whose nature is closely related to the initial composition. To avoid the incorporation into the apatite structure of carbonate ions contained in the starting reagents, it is necessary to use carbonate-free reagents.     

Onboard calibration igneous targets for the Mars Science Laboratory Curiosity rover and the Chemistry Camera laser induced breakdown spectroscopy instrument

Accurate characterization of the Chemistry Camera (ChemCam) laser-induced breakdown spectroscopy (LIBS) on-board composition targets is of prime importance for the ChemCam instrument. The Mars Science Laboratory (MSL) science and operations teams expect ChemCam to provide the first compositional results at remote distances (1.5–7 m) during the in situ analyses of the Martian surface starting in 2012. Thus, establishing LIBS reference spectra from appropriate calibration standards must be undertaken diligently. Considering the global mineralogy of the Martian surface, and the possible landing sites, three specific compositions of igneous targets have been determined. Picritic, noritic, and shergottic glasses have been produced, along with a Macusanite natural glass. A sample of each target will fly on the MSL Curiosity rover deck, 1.56 m from the ChemCam instrument, and duplicates are available on the ground. Duplicates are considered to be identical, as the relative standard deviation (RSD) of the composition dispersion is around 8%. Electronic microprobe and laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) analyses give evidence that the chemical composition of the four silicate targets is very homogeneous at microscopic scales larger than the instrument spot size, with RSD < 5% for concentration variations > 0.1 wt.% using electronic microprobe, and < 10% for concentration variations > 0.01 wt.% using LA ICP-MS. The LIBS campaign on the igneous targets performed under flight-like Mars conditions establishes reference spectra for the entire mission. The LIBS spectra between 240 and 900 nm are extremely rich, hundreds of lines with high signal-to-noise, and a dynamical range sufficient to identify unambiguously major, minor and trace elements. For instance, a first LIBS calibration curve has been established for strontium from [Sr] = 284 ppm to [Sr] = 1480 ppm, showing the potential for the future calibrations for other major or minor elements.     

A possible approach towards spin-polarized transport through single molecule magnets: Mn12 on Au(1 0 0)/Fe(1 0 0)/MgO(1 0 0)

The possibility to use the Au(1 0 0)/Fe(1 0 0)/MgO(1 0 0) system as a substrate for future spin-polarized transport measurements on Mn₁₂ single molecule magnets has been investigated by means of scanning tunneling microscopy and X-ray photoelectron spectroscopy at room temperature. In particular, the stability of the iron layer during a wet chemical preparation of Mn₁₂ monolayers was studied. The results demonstrate that Mn₁₂ can be deposited on Au(1 0 0)/Fe(1 0 0)/MgO(1 0 0) while preserving the metallic nature of the ferromagnetic iron layer which is required as a possible source of spin-polarized electrons in future studies.     

Chemical vapor generation of silver for atomic absorption spectrometry with the multiatomizer: Radiotracer efficiency study and characterization of silver species

Volatile Ag species were generated in flow injection arrangement from nitric acid environment in the presence of surfactants (Triton X-100 and Antifoam B) and permanent Pd deposits as the reaction modifiers. Atomic absorption spectrometry (AAS) with multiple microflame quartz tube atomizer heated to 900 °C was used for atomization; evidence was found for thermal mechanism of atomization. Relative and absolute limits of detection (3σ, 250 μl sample loop) measured under optimized conditions were: 1.4 μg l^? 1 and 0.35 ng, respectively.The efficiency of chemical vapor generation (CVG) as well as spatial distribution of residual analyte in the apparatus was studied by ¹¹¹Ag radioactive indicator (half-life 7.45 days) of high specific activity. It was found out that 23% of analyte was released into the gaseous phase. However, only 8% was found on filters placed at the entrance to the atomizer due to transport losses. About 40% of analyte remained in waste liquid, whereas the rest was found deposited over the CVG system.Presented study follows the hypothesis that the “volatile” Ag species are actually metallic nanoparticles formed upon reduction in liquid phase and then released with good efficiency to the gaseous phase. Number/charge size distributions of dry aerosol were determined by Scanning Mobility Particle Sizer. Ag was detected in 40–45 nm particles holding 10 times more charge if compared to Boltzmann equilibrium. At the same time, Ag was also present on 150 nm particles, the main size mode of the CVG generator. The increase of Ag in standards was reflected by proportional increase in particle number/charge for 40–45 nm size particles only.Transmission electron microscopy revealed particles of 8 ± 2 nm sampled from the gaseous phase, which were associated in isolated clusters of few to few tens of nanometres. Ag presence in those particles was confirmed by Energy Dispersive X-ray Spectroscopy (EDS) analysis.     

The role of gamma irradiation on the extraction of phenolic compounds in onion (Allium cepa L.)

The effect of gamma irradiation on the content of total phenolic compounds, especially quercetin (Q), in onion (Allium cepa L.) skin was investigated. Onion skin extracts contained two predominant flavonoid compounds, Q and quercetin-4′-glucoside (Q4′G). After 10 kGy gamma irradiation, the yield of Q in the extracts increased significantly from 36.8 to 153.9 μg/ml of the extract, and the Q4′G content decreased slightly from 165.0 to 134.1 μg/ml. In addition, the total phenolic compound content also increased after irradiation at 10 kGy, from 228.0 μg/g of fresh weight to 346.6 μg/g; negligible changes (237.1–256.7 μg/g) occurred at doses of up to 5 kGy. As we expected, radical-scavenging activity was enhanced remarkably (by 88.8%) in the 10 kGy irradiated sample. A dose-dependent increase in the peak intensity of the electron paramagnetic resonance (EPR) spectra was observed in all irradiated samples, with a maximum increase at 10 kGy. The intensity relative to that of the control was 0.15, and it increased to 1.10 in 10 kGy irradiated samples. The optimum gamma irradiation dose, which is sufficient to break the chemical or physical bonds and release soluble phenols of low molecular weight in onion skin, is about 10 kGy.     

Silica-coated iron nanocubes: Preparation,characterization and application in microwave absorption

Novel cubic nanocapsules consisting of metallic iron core and amorphous silica shell were fabricated through a simple chemical reduction route followed by a Stöber process. Thus-prepared Fe@SiO₂ nanocubes were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), Fourier transform infrared spectrometer (FTIR), thermogravimetry-differential thermal analysis (TG-DTA), vibrating sample magnetometer (VSM) and scalar network analysis (SNA). Comparing with that of pure iron counterparts, silica-coated iron nanocubes exhibited improved magnetic properties, oxidation resistance and microwave absorption performance. A reflection loss (RL) exceeding ?12 dB was obtained in the frequency range of 8–14 GHz for an absorber thickness of 2 mm, with an optimal RL of ?18.2 dB at 9 GHz. Mechanism of the improved microwave absorption properties of the Fe@SiO₂ composite was discussed based on their magnetic properties and electromagnetic theory.     

Release and enrichment of 44 elements during coal pyrolysis of Yima coal,China

The coal samples were collected from Yima coal district, China. The pyrolysis experiments were carried out in a simulated bed quartz reactor with a heating rate of 20 °C/min. The 44 elements in raw coal and chars were determined by inductively coupled-plasma mass spectrometry instrument (ICP-MS). The release and enrichment behavior of 44 trace elements during coal pyrolysis of Yima coal was studied.According to the transformation behaviors, chemical features and thermal features under different pyrolysis temperatures, the 44 elements can be categorized to 4 groups: light elements (Li and Be), nonmetal elements (Se, As, B, etc.), heavy metal elements (including 24 elements, Cu, V, Co, etc.) and rear earth elements (REE) (14 elements). The results showed that (1) the higher pyrolysis temperatures, the higher release ratio and release ratio of REE are very low; (2) the enrichment ratios of the elements in chars increase by the sequence of nonmetal elements < light elements < heavy metal elements < REE. The nonmetal elements, light elements and a few heavy metal elements will be emitted out from coal during coal pyrolysis and they will pollute environment.     

X-ray micro-imaging by capillary optics

In this work the results on X-ray micro-imaging by means of novel polycapillary optical elements will be presented. To simulate various radiation propagation processes in both single capillary and polycapillary systems, a PolyCAD code was developed. The new experimental results on radiation redistribution by novel capillary lenses in comparison with simulated data will be reported. The images of characterized extended samples (~ 3 mm) were recorded with 6 μm resolution, the maximum provided by CCD. Polycapillary Optics CAD software X-ray tracing Imaging Confocal 02.60.Cb 02.70.-c 41.50. + h 42.15.-i 42.15.Dp 42.30.-d.     

K-line X-ray fluorescence analysis of high-Z elements

X-ray fluorescence analysis with high-energy photons (typically 40–100 keV) is described. Measurement of K-lines from high-Z elements has attractive advantages, which are not available by L-line analysis in normal X-ray region. Through the comparison of excitation methods, it has been found that quasi-monochromatic beams with sufficient intensity and moderate spectral distribution are most suitable for improving the detection limit. Performances of other excitation methods and recent experimental trends are also discussed.     

Characterization of the 3-dimensional microstructure of a graphite negative electrode from a Li-ion battery

The 3-dimensional microstructure of a porous electrode from a lithium-ion battery has been characterized for the first time. We use X-ray tomography to reconstruct a 43 × 348 × 478 μm sample volume with voxel dimensions of 480 nm, subsequent division of the reconstructed volumes into sub-volumes of different sizes allow us to determine microstructural parameters as a function of sub-division size. We show that the minimum size for a representative volume element is about 43 × 60 × 60 μm for volume-specific surface area, but as large as the full sample volume for porosity and tortuosity.