-
Takashi YAMAMOTO, Masaya KONDO
2016 Volume 47 Pages
99-109
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Cr K-edge XANES spectra of various kinds of household articles such as leather products and chromate conversion coatings were recorded with a laboratory-type X-ray absorption spectrometer for quantitative analysis of hexavalent chromium species. The low energy resolution settings were found to be enough and suitable for the quantitative analyses with the spectrometer. The tiny but distinct preedge peak characteristics to hexavalent chromium species could be detected in XANES spectra of chromate conversion coatings with iridescent color, and the ratios of hexavalent to sum of hexa- and trivalent chromium species (Cr6+/(Cr6++Cr3+)) were calculated by the preedge peak height.
View full abstract
-
Hiroaki ANDO, Daisuke KAWAMOTO, Hironori OHASHI, Yasuhiro KOBAYASHI, T ...
2016 Volume 47 Pages
111-118
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
For the preparation of supported Au catalyst by the coprecipitation method, the effect of base(coprecipitating agent) on chemical state of Au coprecipiated in the precursor was investigated by XAFS and 197Au Mössbauer spectroscopy. In this study, Ni(II) ion used as a support metal was characterized by the combination of XAFS, XRD and IR. When Na2CO3 was used as a base, Au was present as Au(III) in the precursor whose support was a NiCO3. On the other hand, when NaOH is used as a base, Au(0) was also present in addition with Au(III) in the precursor whose support was a Ni(OH)2. Consequently, the difference in the chemical state of Au in the precursors is probably dependent on the compounds constructing the supports.
View full abstract
-
E. V. EGOROV, M. S. AFANAS'EV, V. K. EGOROV
2016 Volume 47 Pages
119-124
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Specific features of TXRF spectrometry are considered. The discussion allowed us to single out the critical parameter defining the analytical method efficiently — the exciting flux radiation density. Its increase can be achieved by the planar X-ray waveguide-resonator (PXWR) application for TXRF analysis. Properties of PXWR with simplest design and its composite modification are outlined. It is shown that the composite PXWR including into TXRF spectrometer setup for exciting flux formation allows us to increase its analytical efficiency. Comparison of experimental data obtained at slit-cut system and composite PXWR use is presented.
View full abstract
-
Long ZE, Qiang XU, Hui YANG, Lan WU
2016 Volume 47 Pages
125-130
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Metal corrosion is observed at the Huajiachi, which is a research barge of Zhejiang University at Zhoushan area in China using an SEM-EDX. Corrosion experiments on Q235 specimens using a 3 wt% NaCl solution and 2.7 wt% artificial seawater for comparison.
View full abstract
-
Masaaki HARADA, Aoi SHOKUTA
2016 Volume 47 Pages
131-136
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Diffusion of copper (II) sulfate in the agar was investigated by X-ray fluorescence (XRF), and the diffusion coefficient of Cu2+ was quantitatively determined. And the digital image taken by a web camera was also used to estimate the diffusion coefficient. The obtained values showed rather bigger than those of XRF, but it would be useful for investigating diffusion experiments by XRF.
View full abstract
-
Naoto ICHIMARU, Shinji WATANABE, Hiroaki FURUKAWA, Keijiro SUZUKI, Eis ...
2016 Volume 47 Pages
137-147
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
The United States Pharmacopeia (USP) has established guidelines for general analysis using X-ray Fluorescence (XRF) methodology. Energy Dispersive X-ray Fluorescence (EDX) can be utilized in the screening process for the control of inorganic impurities in pharmaceutical and food products. This study proposes the use of the Scattered X-ray Corrected — Fundamental Parameter (FP) method, thus Background FP method, for quantitation of low ppm level impurity elements in organic samples. The FP method can reduce the need to measure standard samples compared to Calibration curve method. The common condition with scattered X-rays for material correction was selected by each energy region, and these condition was also verified using different volume of cellulose and water samples.
View full abstract
-
Katsumi MARUMO, Kyaw Zaw Htun
2016 Volume 47 Pages
149-166
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
We determined intensities of Ba Kα, Pb Lβ, As Kβ, Zn Kα and Cu Kα of certified standards consisting of sediments and sedimentary rock powder (SS), igneous rock powders (IR) and sulfide ore powder (SO). Among these certified standards, SO was expected to be suitable for X-ray fluorescence (XRF) analysis of contaminated soils containing high Pb, As, Zn and Cu. The ratios of X-ray intensities (I Ba Kα, I Pb Lβ, I As Kβ, I Zn Kα and I Cu Kα) to their element concentrations (X-ray intensity/ concentration) for SS standards were higher than for IR and SO. The ratios of SO standards were significantly lower than those of SS and IR standards. Therefore, it was not possible to make calibration lines for Pb, As, Zn and Cu for XRF analysis using SS and SO standards and/or IR and SO standards.
We prepared contaminated soil samples as data assessment standards for XRF analysis. These data assessment standards were soils contaminated by (1) fallout of dust from smokestacks, (2) waste liquid and incineration ash and (3) sulfide minerals around mineral ore deposits and geothermal areas. These standards covered the data assessment of XRF analysis for the ranges up to 1100 mg/kg for Pb, 620 mg/kg for As, 780 mg/kg for Zn and 730 mg/kg for Cu.
View full abstract
-
Tomoaki KATO, Shigeo SATO, Yoichi SAITO, Hidekazu TODOROKI, Shigeru SU ...
2016 Volume 47 Pages
167-172
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Dislocation evolution of the austenitic stainless steels (NAS316L) and the duplex stainless steels (NAS329J3L) during tensile deformation was investigated by using X-ray diffraction line-profile analysis. In particular, the heterogeneity of dislocation evolution in ferritic and austenitic phases in the duplex stainless steels was focused on for discussing the contribution to the work hardening of each phase. The work hardening of the austenitic stainless steels during tensile deformation was explained by using dislocation density estimated by the line-profile analysis. As for the duplex stainless steels, whereas an increase in dislocation density of the ferritic phase during tensile deformation was rather small, a distinct increase in the dislocation density was confirmed in the austenitic phase. Therefore, the work hardening of the duplex stainless steels can be ascribed to the heterogeneous work hardening in the austenitic phase.
View full abstract
-
Masahiro UCHIDA, Shigeo SATO, Hiroyuki MORI, Yuki ITO, Kazunari MAKI, ...
2016 Volume 47 Pages
173-178
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
To elucidate the relationship between the stress relaxation depending on solute elements in copper alloys and the microstructural recovery, X-ray diffraction line-profile analysis was carried out. The crystallite size, dislocation density, and dislocation arrangement parameter of the Cu-0.057 at% Zr, Cu-1.7 at% Mg, and Cu-27 at% Zn alloys undergoing stress relaxation test were evaluated. It was revealed that the high density of dislocations in the Cu-Zn alloy prompted the stress relaxation. This is one of the reasons why the stress relaxation property of the Cu-Zn alloy is inferior to those of the Cu-Zr and Cu-Mg alloys.
View full abstract
-
Kazuya YANASE, Chizuko KOTERA, Daichi SAWAMURA, Madoka MURAKUSHI, Izum ...
2016 Volume 47 Pages
179-198
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Lelang commandery, one of four commanderies of Han, was located on northwest Korea under the emperor Wu of Han. Han civilization contacted with Japan and three kingdoms of Korea, locating Lelang commandery on northwest Korea. Therefore, analyzing ancient glass artifacts excavated from Lelang commandery is very important to elucidate glass trade in ancient eastern Asia. In this study, 136 glass artifacts from Han dynasty to Western Jin Dynasty (1st c. B.C. ∼3rd c. A.D.) excavated from Lelang commandery were analyzed by using portable XRF spectrometer. The chemical compositions of the glass artifacts from Lelang commandery can be classified into four glass types from their chemical compositions: i.e., potash silicate glass type (K2O-SiO2), high alumina soda lime silicate glass type (Na2O-Al2O3-CaO-SiO2), lead silicate glass type (PbO-SiO2) and lead barium silicate glass type (PbO-BaO-SiO2). The diversity of ancient glass artifacts distributed in Lelang commandery is substantiated by non-destructive chemical analysis with portable analytical instruments. The chemical compositions of some of potash silicate glass artifacts and high alumina soda lime silicate glass artifacts excavated from Lelang commandery were basically similar to those excavated from ancient Japan reported in our previous studies. From these results it is assumed that presence of a direct or indirect trade of glass artifacts between Lelang commandery and ancient Japan.
View full abstract
-
Koichiro ONO, Susumu IMASHUKU, Kazuaki WAGATSUMA
2016 Volume 47 Pages
199-206
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Non-metallic inclusions in metallic materials such as steel are normally analyzed with optical microscope or electron probe microanalyzer (EPMA). These analytical methods require more than several tens of minutes for the measurements. In the present study, we suggested a new analytical technique for rapid identification of the inclusion particles based on scanning electron-cathodoluminescence (SEM-CL). Samples for the SEM-CL analysis was prepared by pressing mixture of copper powder and alumina (Al2O3) powder or silica (SiO2) powder into a form of disc. The luminescence of the samples was captured with a commercially available camera. Measurement durations were less than 30 seconds. We detected blue luminescence for alumina particles and green luminescence for silica particles. In addition, we could distinguish alumina particles and silica particles from luminescent color of the CL image when we carried out SEM-CL analysis for a sample containing both alumina and silica particles.
View full abstract
-
Madoka MURAKUSHI, Daichi SAWAMURA, Kazuya YANASE, Sergey LAPTEFF, Anar ...
2016 Volume 47 Pages
207-224
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
We have been investigating the glass excavated from all over Japan to characterize and classify origin and distribution of the glass in ancient Japan. Central Asia is an important area on the Silk road and some glasses were brought from West Asia and Mediterranean coastal areas. The purpose of our study is to characterize the ancient glass distribution in Central Asia by non-destructive XRF analysis. The origin and distribution of glass were discussed based on their quantitative chemical compositions. The chemical compositions of glass from Kyrgyz and Tajikistan can be classified into three glass types from their major components: i.e., soda lime silica glass (Na2O-CaO-SiO2), potash silica glass (K2O-SiO2) and high alumina soda lime silica glass (Na2O-Al2O3-CaO-SiO2). The trace element signatures of glass excavated from Central Asia were basically similar to those excavated from Japan and Southeast Asia reported in our previous studies. The present study has revealed chemical compositional characteristics of ancient glass excavated from central Asia.
View full abstract
-
Atsushi OHBUCHI, Kotaro OCHI, Yuya KOIKE, Kiyoshi NOMURA, Takayuki KON ...
2016 Volume 47 Pages
225-232
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Fly ash, which was collected at waste incineration facility of Koriyama city in Fukushima prefecture, was treated with the notice No.13 test water (pH=6.20) of Ministry of the Environment and with rain water (pH=5.21). Elements, crystalline phases, and radionuclides in raw fly ash and the treated samples were analyzed by X-ray fluorescence analysis (XRF), X-ray diffraction (XRD), Rietveld refinement, and gamma-ray spectrometry, respectively. It was found that the chlorine compounds of calcium chloride hydroxide (CaClOH), sylvite (KCl) and halite (NaCl) were included as main components in raw fly ash sample. Radiocecium concentrations of 134Cs and 137Cs in raw fly ash sample was 5,791 Bq/kg. The radiocesium decreased to 2,427 Bq/kg after the treatment by extraction methods. It is considered that chlorine compounds were easily dissolved by two kinds of water (pH=6.20 and 5.21). Fly ash containing radiocesium with less than the regulation concentration (8,000 Bq/kg) can be disposed to underground. However, the radiocesium in fly ash may be eluted to environment by rain water for a long term. Fly ash could be utilized as a cement material. The analytical methods of XRF, XRD and radiometry enabled us to easily evaluate for radiocesium contaminated raw fly ash and the solibility. These results would be useful for the treatment of fly ash containing radiocecium in near future.
View full abstract
-
Masataka HIRAO, Issei MAEDA, Momoko IWAI, Naochika KON, Junko HIROKAWA ...
2016 Volume 47 Pages
233-248
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
The authors have been constructing a forensic soil database based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3024 points all over Japan using high-resolution synchrotron X-ray powder diffraction (SR-XRD) and a high-energy synchrotron X-ray fluorescence analyses (HE-SR-XRF) utilizing SR source of SPring-8. In the present study, we first carried out regional characterization of the soils collected from the Hokuriku region in Japan. Both heavy mineral concentration map and heavy element concentration map were prepared and compared with the geological map of the Hokuriku region. As a result, the distribution shows good correspondence with the background geology. Hierarchical cluster analysis was conducted using the semi-quantitative values of heavy minerals and allowed us to classify them into seven groups. Based on multiple comparison methods, we found significant differences in heavy element compositions among these seven groups. Then, since we have completed the analysis of all samples in the current fiscal year, both heavy mineral concentration map and heavy element concentration map in Japan were prepared and compared with the geological map. As a result, the distribution shows good correspondence with the background geology. Therefore, regional characterization using this database is promising. Finally, we collected test samples in the Hokuriku region in Japan and carried out the provenance estimation of these samples as an imaginary case study by comparison with the database. As a result, we could successfully estimate the provenance of these samples, indicating that this database will be useful for criminal investigation.
View full abstract
-
Kenta HAGIWARA, Yuya KOIKE, Mamoru AIZAWA, Toshihiro NAKAMURA
2016 Volume 47 Pages
249-255
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Detection limits of various elements in water using handheld X-ray fluorescence spectrometer were investigated. A sample solution was enclosed in an aqueous sample holder or immobilized with a drip filter paper, and then analyzed by handheld X-ray fluorescence spectrometry. Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, and Pb in water could be determined with mg L-1 levels of detection limit. The method using an aqueous sample holder was advantageous to the elements having high energy of fluorescence X-rays. While, the method using a drip filter paper was advantageous to the elements having low energy of fluorescence X-rays. The concentrations of Ca in natural mineral water samples determined using the above methods were close to the labeled values. The methods did not require a power supply and reagents in any analytical step, therefore it is suitable for the on-site determination of element in water.
View full abstract
-
Ryohei TANAK, Koretaka YUGE, Jun KAWAI
2016 Volume 47 Pages
257-261
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
High-resolution X-ray fluorescence spectra of the Fe Kα line of pure iron and silicon steel were measured. Compared the Fe Kα line of pure iron with silicon steel, the chemical shift was not observable. We addressed the relationship between the chemical shift and the amount of Si in silicon steel in terms of the effect of charge transfer. In order to construct model clusters to be used for electronic state calculation, we performed Monte Carlo simulation and determined atomic arrangement considered from the sample composition with the examples of the Fe-Si binary system. To discriminate the slight difference of chemical state of Fe in silicon steel, the chemical state of Si should be examined instead of Fe.
View full abstract
-
Masaki YAMANASHI, Atsushi GOTO, Kouichi TSUJI
2016 Volume 47 Pages
263-270
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
X-ray fluorescence analysis is widely applied for measuring steel samples because qualitative and quantitative analysis is performed. Recently, X-ray focus optics and X-ray analysis spectrometer are significantly developed. Micro X-ray fluorescence spectrometer with attached X-ray focus optics is used to obtain information of elements in micro area. When quantitative analysis is performed by using X-ray analysis spectrometers, reference materials described the purpose for uses (evaluation of chemical, instrumental methods of analysis and calibration of instrumental methods of analysis) are needed. The certificate of reference materials for X-ray fluorescence analysis does not ensure to apply to micro X-ray fluorescence spectroscopy. Actually, it is known that small inclusions produced in manufacturing process are included in steel reference materials. The segregation in micro size exists in steel reference materials. Since the analytical area of micro X-ray fluorescence spectrometer is micro scale, the segregation in micro size affects the analytical values. In this study, we studied the influence of inclusions to quantitative micro XRF analysis in calibration method. In order to resolve the problem by micro inclusion, multi-point and area analyses were applied. These analysis methods reduced the influence of micro inclusions in steel reference materials.
View full abstract
-
Hikari TAKAHARA, Takao MORIYAMA, Yasujiro YAMADA
2016 Volume 47 Pages
271-277
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Fused bead method is broadly accepted for X-ray fluorescence analysis of minerals, rocks, and refractory materials. This method provides accurate analysis results, because it removes mineralogical and particle size effects and minimizes matrix effect by glass forming. By taking these advantages of fused bead method, single calibration curve applicable for various materials and wide concentration range was investigated. Fused beads were prepared to establish calibration curves of 23 components (Na2O, MgO, Al2O3, SiO2, P2O5, SO3, K2O, CaO, TiO2, V2O5, Cr2O3, Mn2O3, Fe2O3, NiO, CuO, ZnO, Rb2O, SrO, Y2O3, ZrO2, BaO, HfO2, and PbO) from reference materials of minerals and oxides, mixed regents, and standard solutions. Corrections for sample/flux ratio, loss or gain on ignition, and sample thickness which can cause analytical error were considered into the calibration model.
View full abstract
-
Keiichiro SHINOHARA, Masataka OHGAKI
2016 Volume 47 Pages
279-292
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Metal particles contaminated in a lithium ion rechargeable battery cause an internal short circuit that lowers the performance and the safety of batteries. Thus it is essential to control these particles in a manufacturing process of the in-vehicle lithium ion rechargeable battery. Especially, rapid investigations of inspection method of these metal particles contamination are needed to ensure the security of battery. In this study, we examined the applications of X-ray fluorescence analysis and X-ray transmission imaging as an inspection method of lithium ion rechargeable battery to reduce internal short circuit. Three types of samples, (1) a separator, (2) an electrode plate, and (3) an electrode conductive assistant, were used to measure the detection time of the 20 μm contaminant metal particles in diameter within the sample plates having 250 mm x 200 mm in rectangular size and to evaluate the identifying capability by the elemental analyses. As a result, the metal particles were detected in approximately 5 minutes for the separator, approx. 10 min for the electrode plate, and approx. 18 min for the electrode conductive assistant, respectively. Moreover, the subsequent elemental identification was accomplished using the X-ray fluorescence analysis. For these reasons, it was revealed that the metal particle inspection in a lithium ion rechargeable battery can be performed in a short period of time. Therefore, the examined analysis method realizes rapid inspection of battery materials that contributes to a rapid process improvement, furthermore, the reduction of internal short circuit may improve the performance and the safety of batteries.
View full abstract
-
Naoki KAWAHARA, Tsuyoshi MATSUNO, Kouichi TSUJI
2016 Volume 47 Pages
293-300
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
Intensities of fluorescent X-rays from a composite block of Cu and Fe with a vertical border in a confocal micro-XRF configuration are calculated by a simple model but with absorption and secondary excitation effects considered. The simulation indicated that only the secondary excited fluorescent X-rays can be observed with a confocal point outside the sample. Experimental evaluations were also performed and the simulation and the measurements are qualitatively agreed at some points.
View full abstract
-
Nik AFIZA, Yusaku YAMAMOTO, Karen MARUYAMA, Koki NAKAMURA, Shohei YAMA ...
2016 Volume 47 Pages
301-310
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
SiO2-supported small Ni particles were synthesized by the H2 reduction of the SiO2-supported NiO catalyst prepared by the sol-gel method. The small Cu particles were prepared on the Y-type zeolite (FAU) by the liquid-phase reduction after the Cu(II)-ion exchange of FAU. The XAFS measurements revealed that the XANES spectra of the small metal particles are clearly different from those of bulk foils. The particle radius was estimated to be 2 nm and 1 nm for Ni and Cu, respectively, on the basis of the average coordination number determined by the EXAFS analysis. It is clarified that the smoothed absorption edge and the merged absorption peaks just after the absorption edge characterize the XANES spectra of small metal particles. Theoretical calculations of the XANES spectra has been carried out for the metal clusters with the diameter of about 1 nm composed of 55 atoms (Ni55 and Cu55) by means of FEFF 9.6 code. The calculated average XANES spectra reproduced well the characteristics observed for the small metal particles. The XANES spectrum come from the surface atoms with the coordination number less than 12 was calculated independently from that of the core atoms with the coordination number of 12. It has been revealed that the peculiar spectrum of the small metal particles is the result of the larger contribution from the surface atoms.
View full abstract
-
Masahiro OGAWA, Toyonari YAJI, Koji NAKANISHI, Toshiaki OHTA
2016 Volume 47 Pages
311-320
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
In the soft X-ray region,X-ray absorption fine structure (XAFS) spectra are usually taken with the total and partial electron yield (TEY and PEY) modes, as well as the fluorescence yield (FY) mode due to the low transmittance of soft X-rays. Since these three modes have different probing depths, combined use of them provides depth profiling XAFS spectra. The PEY mode is generally performed by the set of a retarding grid and a micro-channel plate. It works successfully in the low energy soft X-ray region below 1000 eV, but it does not provide a surface sensitive PEY spectrum above 1000 eV due to mixing of FY spectra. In this report, a new setup of PEY detector has been developed, which almost completely suppresses the mixing of FY spectra in the higher energy region above 1000 eV. Some typical spectra are shown to demonstrate the effectiveness of the detector.
View full abstract
-
Keisuke YAMANAKA, Masatsugu OISHI, Koji NAKANISHI, Iwao WATANABE, Tosh ...
2016 Volume 47 Pages
321-331
Published: March 31, 2016
Released on J-STAGE: August 26, 2023
JOURNAL
FREE ACCESS
O K-edge and Mn L2,3-edge XAFS spectra of charged/discharged Li2MnO3 positive electrodes were observed to reveal the charge compensation mechanism of Li-rich layered oxides as LIB positive electrode materials. In the charge/discharge measurements, the profile at the first charge process was quite different from that after the first discharge. This result suggests that only the electrochemical reaction at the first charge process is different from any other process. O K-edge and Mn L2,3-edge XAFS spectra at each charge/discharge depth show specific changes, such as changes of pre-edge intensities and/or valence numbers corresponds to each charge/discharge reaction on the Li2MnO3 positive electrode. These XAFS results suggest that the charge compensations are achieved by oxygen desorption from the Li2MnO3 active material in the first charge process, and by the redox reactions of Mn at the lower voltage and O at the higher voltage after the first dischage.
View full abstract