X-Ray Analysis of Multi-Films for Electrochromic Device Application

Multilayer films based on tungsten oxide (WO₃), ITO (indium tin oxide) and CdS were deposited mainly by reactive dc magnetron sputtering onto glass substrates for electrochromic application. The thin films were analyzed by means of XPS (X-ray photoelectron spectroscopy), GIXD (grazing incidence X-ray diffraction) and XRD (X-ray diffraction). XRD and XPS results confirmed that the films were WO₃, CdS and ITO, respectively. The surface and interface of the CdS/ITO bi-layered film was studied by GIXD in different incidence angles. Detailed results about the amorphous characterization of the films during room temperature growth and post annealing are given.     

Identification and Classification of Iridescent Glass Artifacts with XRF and SEM/EDX

 Art Nouveau (Tiffany, Loetz) and modern (Jack Ink, Strini Art Glass) iridescent glass fragments were characterized using energy dispersive X-ray fluorescence analysis (EDXRF) and energy dispersive X-ray microanalysis in a scanning electron microscope (SEM/EDX) in combination with factor analysis in order to obtain clustring. A character istic of Tiffany glass fragments is leaded bulk glass, whereas in the case of Loetz K-Ca-Si bulk glass could be determined. Modern glass fragments show a high amount of Na (7 wt% in the bulk of Jack Ink) and 0.6–1.5 wt% Sr in the bulk of Strini Art Glass. The contents of Si and Ca are similar to Loetz glass. Furthermore, the differences in the structure of the glass artifacts could be determined. The cross-sections of Tiffany show a layered structure of the bulk without a specific surface layer whereas the cross-sections of Loetz glass reveal a homogeneous bulk material with one or two homogeneous surface layers in the BE-image. In the case of the Jack Ink a homogeneous bulk glass and an inhomogeneous multilayered surface could be determined. Strini Art Glass show a homogeneous bulk glass and a homogeneous surface layer in the backscattered electron image.     

The influence of X-ray resonant Raman scattering effects on the detection of copper(II) tetrasulphonated phthalocyanine (CuTSPc) thin-films deposited on gold electrodes

The influence of X-ray resonant Raman scattering on the detection capabilities of copper(II) tetrasulphonated phthalocyanine (CuTSPc) thin-films on gold electrodes has been investigated by means of synchrotron radiation X-ray fluorescence. In particular the paper focuses on the influence of the excitation energy in the relative narrow energy region of 9.2 to 11.7 keV on the detection limits and the peak-to-background ratios of copper.     

Characterization of an energy dispersive X-ray fluorescence imaging system based on a Micropattern Gaseous Detector

An energy dispersive X-ray fluorescence (EDXRF) imaging system based on a Micropattern Gas Detector has already shown good results for different applications. An X-ray tube, a pinhole camera and a Micro-Hole and Strip Plate (MHSP) based detector are the main components of the experimental system. The detector uses an MHSP in a Xe atmosphere at 1 bar, and acting as a photon counting device, i.e., it is capable to record each single event retaining the energy and the interaction position (2D-sensitive detector) information of the incident photon, demonstrating to be a promising device for EDXRF imaging applications. This work presents studies of energy resolution, energy linearity and spatial resolution/elemental mapping as a function of image magnification of the system.     

砷化镓半导体表面自然氧化层的X射线光电子能谱分析

用X射线光电子能谱(XPS)，测量了Ga3d和As3d光电子峰的结合能值，指认了砷化镓(GaAs)晶片表面的氧化物组成，计算了表面氧化层的厚度，定量分析了表面的化学组成；比较了几种不同的砷化镓晶片表面的差异。结果表明：砷化镓表面的自然氧化层主要由Ga2O3、As2O5、As2O3和单质As组成，表面镓砷比明显偏离理想的化学计量比，而且，氧化层的厚度随镓砷比的增大而增加；溶液处理后，砷化镓表面得到了改善。讨论了可能的机理。     

X-ray fluorescence mercury determination using cation selective membranes at sub-ppb levels

In the present work a method for the determination of mercury at trace levels by energy dispersive X-ray fluorescence (EDXRF) is introduced. Mercury ions were concentrated on cation selective membranes that have been prepared on Mylar^® thin film substrate, immobilized on plastic cups. The produced membranes were immersed in water solutions containing low concentrations of mercury. The membranes were left to equilibrate in 1000 mL of mercury solutions and were analyzed by EDXRF. The effects of various experimental parameters were examined. Minimum detection limits of pg mL⁻¹ (ppt) (0.069 ng mL⁻¹ for ASTM Type I water and 0.064 ng mL⁻¹ for seawater) and good linearity were achieved.     

Assessment of the essential element and heavy metal content of edible fish muscle

The aim of this work was to determine the concentrations of some essential and toxic elements in the muscle of ten species of commercial fish consumed in Portugal. We combined two different techniques for determination of the elements—energy-dispersive X-ray fluorescence (EDXRF) was used to quantify K, Ca, Fe, Zn, Se, Rb, and Sr and flame atomic-absorption spectrometry for analysis of Cr, Ni, Cu, Cd, Hg, and Pb. The latter technique was used because of its higher sensitivity, because these elements were not detected by EDXRF. The results obtained show a similar pattern for the trace elements. K and Ca are present at the highest concentrations in all the samples studied, from 0.6–1.3% and from 0.04–0.08%, respectively, followed by Zn, Fe, Sr, Se, and Rb. Sr is present at higher concentrations than Rb in all the species studied except meagre. Concentrations of the elements in octopus do not follow this pattern—Fe is present at a higher concentration than Zn. Low concentrations of Cr (0.66–1.5 g g^–1), Ni (0.11–0.24 g g^–1), Cd (0.01–0.08 g g^–1), Hg (0.49–2.74 g g^–1), and Pb (0.02–0.06 g g^–1) were observed in all the samples analysed. The concentration of Hg was highest in Helicolenus dactylopterus—5.4 g g^–1 in one sample.     

New sights into the electrochemical interface provided by in situ X-ray absorption fine structure and surface X-ray scattering

Various important processes, such as electron transfer reactions, adsorption/desorption, solvation/desolvation, and formation/cleavage of chemical bonds, take place at electrolyte/electrode interfaces during electrocatalytic reactions. Those processes have been understood on the basis of changes in the surface composition, atomic arrangement, and molecular and electronic structures of the interfaces by using various in situ analysis techniques. To date, in situ analysis and observation of those interfacial processes at an ideal single-crystal surface are indispensable not only for fundamental understanding of the reaction mechanism but also for rational design of the highly efficient and durable electrocatalytic materials. Here, historical and recent progress of in situ studies on electrocatalytic reactions is briefly reviewed with a focus on two major techniques, X-ray absorption fine structure and surface X-ray scattering.     

SEM–EDX and SAM–AES Investigations on Rochow Contact Masses

Appropriate Rochow contact masses have been investigated by the spatial resolution techniques SEM–EDX and SAM–AES. The results gave evidence of the existence and the catalytic action of (X-ray)-amorphous copper–silicon (Cu–Si) surface species, i.e. extremely highly dispersed particles or two-dimensional species. The well-known Rochow promoter zinc seems to act as a moderator rather than as a real accelerator. It ensures a stable rate for the reaction by neutralizing the detrimental action of silicon impurities. The silicon impurities make the whole of the silicon surface reactive and in this way cause a general blockade of the silicon surface by inactive copper species. Zinc localizes the reaction. The silicon surface remains partly free, and active Cu–Si surface species can be formed by lateral diffusion of copper onto the silicon surface that is still free. © 1997 by John Wiley & Sons, Ltd.     

Analytical determination of colouring elements and of their compounds in glass beads from graveyards of the Merowings time

428 Monochrome beads from mainly female graves excavated at Groß-Gerau, Pleidelsheim and Weingarten (Germany) were examined by non-destructive methods, i.e. energy-dispersive X-ray fluorescence analysis (EDXRF), wavelength-dispersive X-ray fluorescence analysis (WDXRF) with fundamental parameter evaluation, and X-ray diffraction analysis. The results obtained by EDXRF were compared with those for beads from Donaueschingen and Eichstetten, published in former papers. In most cases the results obtained by WDXRF show very high contents of the colouring compounds, corresponding to a low glass quality. The diffraction measurements show crystalline colouring compounds at the surface of the glass beads that can be characterized as Pb₂SnSbO_6.5 for the yellow beads and as Cu₂O for the ochre beads.     

Equilibrium,kinetic and thermodynamic studies of copper adsorption onto poly(n-vinylpyrrolidone) modified clay

We demonstrated in this study the removal of copper ions from aqueous solutions by a new and cost efficiency adsorbent based on poly(N-vinylpyrrolidone) modified sodium bentonite. The X-ray diffraction analysis confirmed that the poly(N-vinylpyrrolidone) is well intercalated in the clay inter-sheets. Adsorption of copper was analyzed by the atomic absorption spectroscopy technical.

Quantitative removal of copper in aqueous solution and the optimum conditions in batch experimental set-up were attained by following searching effects such as contact time, initial metal concentration, pH and temperature.

The elimination of this pollutant by this a new composite reached 3.27 mg.g^?1, which is more important than the amount of copper adsorbed by the non-modified clay (1.5 mg.g^?1). The experimental results showed that the equilibrium and shaking time was attained within 05 min. The better retention capacity of copper was obtained at pH between 4 and 5.8.

Equilibrium data were well fitted with the Langmuir, Freundlich and Elovich models.

Also, the pseudo first order and pseudo-second-order were also applied. The experimental data follow well the pseudo-second-order kinetics. The thermodynamic of this new adsorbent of copper shows spontaneous and exothermic process with a negative value of ΔS.     

Nickel and copper complexes of cyclopropyltetrazole: crystal structures of [Ni(C3tz)6](BF4)2 and [Cu(C3tz)6](BF4)2

Cyclopropyltetrazole (C₃tz) and its nickel(II) and copper(II) complexes [M(C₃tz)₆](BF₄)₂] were isolated and characterized by elemental analyses, electronic spectroscopy, molar conductances, magnetic susceptibilities and single-crystal X-ray analyses.     

Ligand directed synthesis of a unprecedented tetragonalbipyramidal copper (II) complex and its antibacterial activity and catalytic role in oxidative dimerisation of 2-aminophenol

In pursuit of the significant contribution of copper ion in different biological processes, this research work describes the synthesis, X-ray structure, Hirshfeld surface analysis, oxidative dimerization of 2-aminophenol and antibacterial activity of a newly designed copper (II)-Schiff base complex, [Cu( L )₂] (1), [Schiff base (H L ) = 2-(2-methoxybenzylideneamino)phenol]. X- ray structural analysis of 1 reveals that the Cu (II) complex crystallizes in a cubic crystal system with Ia-3d space group. The Cu (II) centre adopts an unprecedented tetragonal bipyramidal geometry in its crystalline phase. The Schiff base behaves as a tridentate chelator and forms an innermetallic chelate of first order with Cu (II) ion. The copper (II) complex has been tested in the bio-mimics of phenaxozinone synthase activity in acetonitrile and exhibits good catalytic activity as evident from high turnover number, 536.4 h⁻¹. Electrochemical analysis exhibits the appearance of two additional peaks at −0.15 and 0.46 V for Cu (II) complex in presence of 2-AP and suggests the development of AP⁻/AP^•− and AP^•−/IQ redox couples in solution, respectively. The presence of iminobenzosemiquinone radical at g = 2.057 in the reaction mixture was confirmed by electron paramagnetic resonance and may be considered the driving force for the oxidative dimerisation of 2-AP. The existence of a peak at m/z 624.81 for Cu (II) complex in presence of 2-AP in electrospray ionization mass spectrum ensures that the catalytic oxidation proceeds through enzyme-substrate adduct formation. The copper (II) complex exhibits potential antibacterial properties against few pathogenic bacterial species like Staphylococcus aureus, Enterococcus and Klebsiella pneumonia and scanning electron microscope studies consolidates that destruction of bacterial cell membrane accounts on the development of antibacterial activity.     

Lead post-mortem intake in human bones of ancient populations by (109)Cd-based X-ray fluorescence and EDXRF

In this work we measured the lead concentration in human bones of Middle Age by means of a portable X-ray fluorescence system based on ¹⁰⁹Cd radioactive source. The detection system consists on a Ge hyperpure detector. This system, conceived for in vivo Pb analysis in bone, is portable, non-destructive and is based on lead K lines detection.

The analysed bones are part of two collections of bones both from the end of Middle Age and submitted for some years to a lead polluted burial environment. The bones of one collection were buried initially on the soil in a convent, in Lisbon (Portugal) and further on, kept in a lead coffin for around 100 years. The second collection contains bones buried permanently on the soil around an old church on the south of Portugal. This place became a parking car for around 20 years.

In this work we studied the distribution of Pb in cortical bone, and trabecular regions from the outside surface to the inner part of the bone and the results are compared with the obtained ones by energy dispersive X-ray fluorescence (EDXRF).

The obtained values present a strong contamination of Pb in spongy bones kept in the lead coffin with concentrations ranging from 250 to 350 μg Pb/g bone mineral, and 4 to 7 μg Pb/g bone mineral for bones buried in the soil. Good agreement was observed between the results obtained by the two techniques.     

Copper(I) and mercury(II) halide complexes of 1,2-bis(diphenylthioylphosphino)hydrazine

The reaction of 1,2-bis(diphenylthioylphosphino)hydrazine (L) with copper(I) and mercury(II) halides affords the complexes, [{CuLX}₂] (X = I, Br or Cl), [HgLX₂] (X = Cl or Br) and the tetrametallic complex, [{L(HgI₂)₂}₂]. Single crystal X-ray structures have been performed on the uncoordinated ligand, L, as well as the complexes [{CuLX}₂] (X = I, Br and Cl), [HgLBr₂] and [{L(HgI₂)₂}₂. The molecules of L exist as dimers as a result of pairs of N–HS hydrogen bonds. The copper(I) complexes are centrosymmetric dimetallic species, the two copper atoms being bridged by L and the X atoms. In all cases the coordination sphere around the Cu atoms is approximately trigonal pyramidal with an ‘S₂X₂’ donor set. The complex, [HgLBr₂], is a distorted tetrahedral monomer with an ‘S₂Br₂’ donor set and L acting as a bidentate thus forming a seven-membered chelate ring. The tetramercury iodo complex, [{L(HgI₂)₂}₂], contains two ‘L(HgI₂)₂’ units linked centrosymmetrically via an I atom from each moiety. The geometry around the Hg atoms is distorted tetrahedral. The influence of hydrogen bonding between the hydrazine backbone hydrogens of L and the coordinated halide ions in for the structures of the metal complexes is discussed.     

便携式能量色散X射线荧光光谱仪在土壤检测中定方法研究

能量色散X荧光光谱仪至今还没有形成统一的国家检定规程.因此,根据仪器的实际检定要求,参考相关仪器的检定规程,对能量色散X荧光光谱仪的检定方法进行了深入的研究和探讨,提出了能量色散X射线荧光光谱仪的检定方法.     

Combined analysis methods for investigating titanium and nickel surface contamination after plasma deep etching

Plasma etching techniques can result in damage and contamination of materials, which, if not removed, can interfere with further processing. Therefore, characterisation of the etched surface is necessary to understand the basic mechanisms involved in the etching process and enable process control and cleaning procedures to be developed. A detailed investigation by means of the combined use of scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM/EDS), X-ray photoelectron spectroscopy (XPS) and optical microscopy (OM) has been carried out on deep titanium trenches etched by plasma. This innovative approach has provided a further insight into the microchemical structure of the surface contamination layer on both the titanium and the nickel hard mask surfaces. The described experiments were conducted on 25 to 100-μm wide trenches, first etched in bulk titanium by an optimised Cl₂/SF₆/O₂-based inductively coupled plasma process, through an electroplated nickel hard mask. The results allow to identify chlorine, fluorine and carbon as the main contaminating agents of the nickel mask and to associate three oxidation states around the etched trenches highlighting certain specific aspects related to the passivation mechanism. These observations reinforce the scientific relevance of the combined use of complementary optical and imaging analytical techniques.     

EDXRF as an analytical tool in art: Case studies from pigment identification and treatment assessment

Energy dispersive X-ray fluorescence (EDXRF) was employed for the identification of pigments decorating Hellenistic figurines, and the assessment of the efficiency of a treatment with barium hydroxide applied to stone. Elements present in the colored areas of the figurines, as well as the treated stone was identified by EDXRF. These data together with complementary information obtained by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD) led to the identification of several precious pigments. As far as the treatment efficiency is concerned, EDXRF analysis revealed that barium is unevenly distributed on the treated surface and reaches a maximum depth of 2.5 mm.     

EDXRF as an analytical tool in art: Case studies from pigment identification and treatment assessment

Energy dispersive X-ray fluorescence (EDXRF) was employed for the identification of pigments decorating Hellenistic figurines, and the assessment of the efficiency of a treatment with barium hydroxide applied to stone. Elements present in the colored areas of the figurines, as well as the treated stone was identified by EDXRF. These data together with complementary information obtained by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD) led to the identification of several precious pigments. As far as the treatment efficiency is concerned, EDXRF analysis revealed that barium is unevenly distributed on the treated surface and reaches a maximum depth of 2.5 mm.     

Oxidation behaviour of precipitation hardened steel TG,X-Ray,XRD and SEM study

In the present work the oxidation behavior of ageing treated steel was examined up to 1000°C in different environments (O₂ and CO₂) and with different heating rates. The examination was conducted by means of thermogravimetric analysis, scanning electron microscopy and X-ray diffraction. In this study it was deduced that in the case of O₂ an oxide scale is formed on top of the steel. The oxidation is uniform and the growth of the scale is more intent at low heating rate. It consist of different Fe, Mn, Mo and Cr oxides which are adjusted in the form of layers. This phenomenon was explained by the different diffusion coefficients of each metal in the already formed scale. Regarding the oxidation in CO₂, the scale formation takes place at a lower temperature than in the case of O₂. Hence the examined substrate is more vulnerable in CO₂.