Intensity Ratio of Kß/Kα in Selected Elements from Mg to Cu, and the Chemical Effects of Cr Kα1,2 Diagram Lines and Cr Kß/Kα Intensity Ratio in Cr Compounds.

Kα,ß X-ray lines from photon excitation were measured in selected elements from Mg to Cu using a high-resolution double-crystal X-ray spectrometer with a proportional counter, and the Kß/Kα intensity ratio for each element was obtained, after correcting for self-absorption, detection efficiency, and crystal reflectance. This intensity ratio increases rapidly from Mg to Ca but, in the 3d elements region, the increase becomes slower. This is related to the intensity of the Kß line involving valence electrons. The slow increase of this ratio in the 3d elements region is thought to be due to the correlation between 3d and 4s electrons. Moreover, the chemical shifts, FWHM, asymmetry indices, and Kß/Kα intensity ratios of the Cr compounds, due to different valences, were also investigated using the same double-crystal X-ray spectrometer. The chemical effects were clearly observed, and the Kß/Kα intensity ratio was found to be compound-dependent for Cr.

X-ray absorption fine structure combined with x-ray fluorescence spectrometry. Part 15. Monitoring of vanadium site transformations on titania and in mesoporous titania by selective detection of the vanadium K alpha1 fluorescence.

X-ray absorption fine structure combined with X-ray fluorescence spectrometry was applied to various V+TiO2 hybrid samples. Emitted V K alpha1 fluorescence from the sample was selectively counted by using a high-energy-resolution (0.4 eV) spectrometer equipped with a Ge(331) crystal. Two advantages of this method, extremely high signal/background ratio and the compatibility of measurements in the atmosphere of reaction gas (in situ study in relation to heterogeneous catalysis), were effective at the V K-edge. Structure transformation of the V sites was spectroscopically followed for the V/TiO2 catalyst. The monooxo tetrahedral vanadate site was demonstrated to exist at 473 K. It transformed into dispersed species of 5-fold coordination in ambient air and further into polymeric VO(x) species in 0.85 kPa of water at 290 K. In the presence of 3.2 kPa of 2-propanol, dissociative adsorption of 2-propanol on the dispersed V species was strongly suggested at 290-473 K. In situ structure changes of V sites on TiO2 were reported by means of XAFS for the first time. The V(V) sites for the V/TiO2 catalysts were essentially identical with those for V supported on mesoporous (high-surface-area) TiO2 and V-TiO2 sample prepared by the sol-gel method. However, predominant V(IV) sites were found for mesoporous V-TiO2. The V(IV) sites substituted on the Ti sites of TiO2. When the molar ratio of V/Ti increased from 1/100 to 1/5.0, major octahedral V sites in the TiO2 matrix looked to transform into tetrahedral ones.

A study of the cascade Auger process using a cluster calculation.

The Auger process on shallow levels, caused by the Auger process in deeper levels, called "cascade Auger process", were studied. From the measurement result, the cascade Auger process can be clearly observed by the excitation of X-ray tubes instead of a synchrotron radiation source. Applying a theoretical investigation with a cluster calculation to the spectral change of the Ag M(VI,V)VV peak, it was theoretically shown that the cascade Auger process should be correct for explaining the observed spectral change. In addition, it pointed out the existence of a cascade Auger process caused by holes left by the Coster-Kronig process on deeper levels. For the first time the measurement of this process was successful using X-ray tube excitation.

The theoretical study of si core levels for the change of oxidation state.

The investigations of Si 1s and 2p photoelectron spectra of a poly-Si plate with natural oxide layers based on high energy excitation using X-ray tubes with three kinds of target (Mg K(alpha), Zr L(alpha) and Ag L(alpha)) and on the theoretical calculations using DV-Xalpha were presented. From the comparison between the shift values of Si 1s and 2p corresponding with the metal and oxide, it was found that 1s shift is larger than 2p shift. From the discussion on the cluster calculation, the data revealed that the direction of chemical shift is dominated by the change of the population of 3s/3p or 3d independently.

X-ray fluorescence analysis of Cr(6+) component in mixtures of Cr(2)O(3) and K(2)CrO(4).

X-ray fluorescence analysis using Cr K(alpha) spectra was applied to the determination of the mixing ratio of Cr(6+) to (Cr(6+) + Cr(3+)) in several mixtures of K(2)CrO(4) and Cr(2)O(3). Because the powder of K(2)CrO(4) contained large particles that were more than 50 microm in diameter, it was ground between a pestle and a mortar for about 8 h. The coarse particles still remaining were removed by using a sieve with 325-mesh (44 microm) in order to reduce the difference in absorption effects between emissions from Cr(6+) and those from Cr(3+). The mixing ratio, K(2)CrO(4)/(K(2)CrO(4) + Cr(2)O(3)), of the five mixtures investigated is 0.50, 0.40, 0.20, 0.10, and 0.05 in weight, respectively. Each spectrum obtained was analyzed by decomposing it into two reference spectra, those of the two pure materials, K(2)CrO(4) and Cr(2)O(3), with a constant background. The results for the mixtures containing K(2)CrO(4) of more than 20 wt% are that the relative deviation from the true value is less than approximately 5%. On the other hand, when the content of K(2)CrO(4) decreases to less than 10 wt%, the relative deviation gets so large as 20 - 25%. The error coming from a peak separation of spectrum involved in our results were estimated by applying our method to five sets of data for each mixture computationally generated, taking into account the uncertainty in total counts of real measurements.

High-resolution and high-intensity powder diffractometer at BL15XU in SPring-8.

A new ultra-high-resolution powder diffractometer for synchrotron radiation has been constructed at beamline BL15XU, SPring-8. The two-axis diffractometer is optimized for high-flux and high-coherent X-ray beams, which are provided by combining a planar undulator and a large offset rotated-inclined Si(111) double-crystal monochromator. The optics design of the diffractometer is based on transmission geometry, which employs a capillary specimen and reflection geometries using a flat-plate specimen. The intensity data are collected using a 2theta step-scan technique in both geometries. The diffractometer can be arranged in a variety of optical configurations, e.g. simple receiving slits, flat crystal analyzer of Ge(111) or Si(111), and in-vacuum-type long horizontal parallel slits. A minimum full width at half-maximum against 2theta was 0.00572 degrees at lambda = 0.63582 A for the (200) reflections from Si powder in the transmission geometry employing the Ge(111) crystal analyzer. A wide temperature range (32-900 K), which is controlled by a He/N(2) gas stream system, is available. 288 structure parameters of a zeolite ZSM-5 sample have been demonstrated to successfully refine with a R(wp) value of 6.96% by a Rietveld analysis of the high-resolution powder diffraction data from a 1 mm-diameter capillary specimen.

Non-existence of positive glitches in spectra using the YB(66) double-crystal monochromator of BL15XU at Spring-8.

YB(66) is suitable for dispersing synchrotron radiation in the 1-2 keV energy range with a 2d lattice spacing of 1.17 nm. When used with an undulator there are no positive glitches at 1385.6 and 1438 eV in spectra dispersed by a YB(66) 400 double-crystal monochromator as observed using bending-magnet or wiggler beamlines. The transmission function of a YB(66) double-crystal monochromator has been measured by means of a Si PIN photodetector, and X-ray absorption near-edge structure (XANES) of Mg, Al and Si were measured at high resolution. From all of these experiments it has been clarified that a YB(66) double-crystal monochromator is well suited for soft X-ray beamlines on third-generation light sources.