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One simple example of a rapid flow-through analysis (RFA) system based on ion-selective optode detection was demonstrated, and its performance was discussed. The RFA is a flow analytical method based on a reagentless analyte flow injection system combined with an analyte selective monitor/sensor such as an optical chemical sensor (optode) involving mathematical response simulation using a semi-empirical theoretical response equation. The response of RFA with optode detection can basically be expressed by the equation derived from Fick’s law of diffusion and Kubelka–Munk’s law, and two other variable parameters in relation to the experimental response. Mathematically simulated results using the proposed equation indicated that the equation can be useful for the prediction of the flow analytical response. In the present demonstration of RFA, highly selective ionophores based on 16-crown-5 derivatives were used for the ion-sensing component of the optode for sodium ion determination. A sodium ion-selective optode based on C14-DD16C5 and KD-A3 exhibited high selectivity for sodium ion over potassium ion, with a selectivity coefficient ( log K i , j opt ) of −2.6. This optode responded to sodium ion in the concentration range from 10 −5 to 10 −1 M at pH 8.0 by measuring the absorbance change at 510 nm in the sensing phase of the optode. The RFA system equipped with a sodium ion-selective optode offers a reagent-less advanced ion-determination methodology for conventional flow injection analysis.

We have investigated the chemical bonding states at the surfaces of La1.5Ba0.5SrCu2O6-d annealed under CO, CO2 and SO2 gaseous conditions, by using X-ray photoelectron spectroscopy (XPS). The C 1s and S 2p core-level data obtained from XPS indicate that each adsorbate exists as CO3δ- and SO4δ- on the reaction surfaces, respectively. The Cu 2p XPS spectra suggest that the reaction surfaces of the cuprate donate the electrons to the adsorbates and that the hybridizations of Cu(3d)-O(2p) orbitals change.

The surface chemical binding states of NO-intercalated La1.5Ba0.5SrCu2O6-δ were investigated by X-ray photo-electron spectroscopy (XPS) analysis. The N1s XPS spectra suggested the occurrence of surface adsorption of NO2- and NO3- groups. The chemical shift of the Cu2p XPS peak indicated decreasing hole concentrations at the level of O2p with NO intercalation in contrast to the case of LaBaSrCu2O6-δ. In addition, the surface intercalation of NO-produced a chemical shift of the Ba3d and Sr3d XPS peaks. These results suggested that the Ba content affected the surface groups on the cuprates.

The difference between La-deficient and Sr-substituting effects for La in LaCoO${}_{3}$ has been investigated by using x-ray photoelectron spectroscopy (XPS). On the basis of the relationship between the intensity of the ${}^{2}{T}_{2}$ line and the amount of low-spin Co${}^{3+}$ ions in these compounds, it is pointed out that La${}_{0.9}$CoO${}_{3\ensuremath{-}\ensuremath{\delta}}$ is in a highly covalent low-spin state and La${}_{0.8}$Sr${}_{0.2}$CoO${}_{3\ensuremath{-}\ensuremath{\delta}}$ is in a mixed spin state. From the Co $2p$ and valence-band XPS results, it is pointed out that the electronic state of La${}_{0.9}$CoO${}_{3\ensuremath{-}\ensuremath{\delta}}$ is quite different from that of Sr-substituting La${}_{0.8}$Sr${}_{0.2}$CoO${}_{3\ensuremath{-}\ensuremath{\delta}}.$ In order to explain the difference between La-deficiency and Sr-substitution effects in valence controlling of LaCoO${}_{3}$, it is considered that Sr substitution produces the Co $3d$ holes and La deficiency yields the O $2p$ holes.

The NOx intercalation properties of La2-xBaxSrCu2O6-δ was investigated by thermal analysis (TGA-DTA) and X-ray photoelectron spectroscopy (XPS) analysis. The results of thermal analysis showed that the NOx absorbability was increased by Ba substitution. The N1s XPS spectra suggested the surface adsorption of NO2- and NO3- groups corresponding to NOx trapped by oxygen vacancies. The chemical shift of Cu2p XPS peak indicated the increasing hole concentrations at the level of O2p with NOx intercalation. Also, the surface intercalation of NO2 resulted the chemical shift of Ba3d and Sr3d XPS peaks.

Disulfide-bridged binuclear ruthenium complexes, [{RuCl(P(OMe)3)2}2(μ-Cl)2(μ-S2)] (1), [{RuCl(P(OMe)3)2}(μ-Cl)2(μ-S2){Ru(CH3CN)(P(OMe)3)2]+ ([2]+), [{Ru(CH3CN)3(P(OMe)3)2}2(μ-S2)]3+ ([3]3+), [{Ru(CH3CN)(P(OMe)3)2}2(μ-Cl)2(μ-S2)]2+ ([4]2+), and [{Ru(CH3CN)3(P(OMe)3)2}2(μ-S2)]4+ ([5]4+), have been synthesized, and their crystal structures have been solved. Compounds 1, [2]+, and [4]2+ have a triply bridged RuIII (μ-Cl)2(μ-S2)RuIII core, in which the S22- ligand bridges the two Ru atoms in a cis configuration. Compounds [3]3+ and [5]4+ have a singly bridged trans-RuSSRu core, whereby [3]3+ corresponds to a one-electron reduced form of [5]4+. Compound [3]3+ is the first example of a well-characterized mixed-valent compound with a trans-MSSM core, where M is any metal. All the compounds have intense absorption bands at around 700 nm, which can be explained for [3]3+ and [5]4+ as a π−π* transition of the distinct trans-RuSSRu core. Resonance Raman spectroscopy of 1, [2]+, and [3]3+ and comparison with several l...

Flow-through type calcium ion selective optodes based on novel neutral ionophores and a lipophilic anionic dye were developed. The novel calcium ion selective neutral ionophores designed and synthesized were double-armed diazacrown ether compounds possessing glycolic amides as the binding arms. Cation sensing material was prepared by coating pellicular-type ODS (octadecylsilica) beads with a lipophilic organic liquid which incorporates a novel neutral calcium ionophore and a lipophilic anionic dye of the diphenyl amine type. These beads were packed in a flow-through optical cell, and the Ca 2+ measurement was performed to measure the absorbance change of the sensing beads at 516 nm. The best optode tested exhibited a good response to calcium ions in the concentration range from 10 −7 M to 10 −1 M with 0.05 M Tris-HCl of pH 7.0 as the flowing buffer solution. This optode showed excellent Ca 2+ selectivity of over 10 −4 in selectivity coefficient values ( k i,j opt. ; i = primary ion (Ca 2+ ); j = interfering ion) against Na + , K + and Mg 2+ which are primary interferents for human serum analysis. Sensor response theory, response time, selectivity, and application to the determination of calcium ion concentration in human serum were also discussed together with experimental results.

We studied the adhesion of a silicon dioxide film, formed from silane and nitrous oxide gas by plasma‐enhanced chemical vapor deposition, to a polycarbonate substrate and the bonding between the film and the substrate by x‐ray photoelectron spectroscopy. Adhesion of the SiO2 film to the polycarbonate increases with increasing SiH4 flow rate. All SiO2 film squares produced at a SiH4 flow rate of 10 standard cm3 min−1 exhibited good adhesion to the substrate. An analysis of the x‐ray photoelectron spectra indicates that more phenyl groups are decomposed as adhesion increases. The bonding between the SiO2 film and the polycarbonate substrate is discussed on the basis of x‐ray photoelectron spectroscopy. The Si–O–C bonding between SiO2 and polycarbonate results in good adhesion between the film and the substrate.

Several 14-membered thia crown ether ionophores having a bulky block subunit were synthesized, and their chemical structures and ion selectivities were examined in detail when these compounds were used as an ion-sensing component of an ion-selective electrode. The ionophores of both cyclic and noncyclic thia ethers exhibited a high selectivity for silver ion (Ag(+)), in which the sulfur atom in the ionophore molecule plays a role as the effective coordination donor site for the silver ion. The best Ag(+)-selective electrode was prepared with the 14-membered thia crown ether having one sulfur atom, three oxygen atoms, and a bulky pinan subunit. The ion selectivity of this electrode for Ag(+) was over 10(4) times that for other metal cations. In the case where the sulfide in the thia ether ionophore was changed to sulfoxide by oxidation, ion selectivity for mercury ion became higher; therefore, the sulfoxide was found to be an effective coordination site for the mercury ion. The ion selectivity features of noncyclic sulfide, sulfoxide, and sulfone were also examined and compared with the results of the cyclic and noncyclic thia ethers.

Experiments on x-ray photoelectron spectroscopy of ${\mathrm{Bi}}_{2}$${\mathrm{Sr}}_{2}$${\mathrm{Ca}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Y}}_{\mathit{x}}$${\mathrm{Cu}}_{2}$${\mathrm{O}}_{\mathit{y}}$ were performed to investigate the change of valence of each atom and the distribution of Y atoms on the cation sites. The core-level binding energies of Sr and Y increased with increasing Y content and that of Bi did not change. The average valence of Cu was above 2 for 0.0\ensuremath{\le}x\ensuremath{\le}0.5 and below 2 for 0.8\ensuremath{\le}x\ensuremath{\le}1.0. Y atoms were substituted for the cations between the adjacent Cu-O planes.

チタン,窒素,シリコン化合物について二次イオン質量分析法(SIMS)による化合物の同定と深さ方向分析について検討を行った.セシウムイオンを一次イオン種とした際の各種化合物の二次イオンのうち,特異的に化合物の存在を示すイオンを選択し,そのイオンを用いた深さ方向分析法を窒化ケイ素-金属接合界面の生成物分布分析に適用した結果,以下の知見が得られた.1)窒化チタンの存在を示す特異イオンとしては,m/z=62, 110, 124, 195がよい.2)ケイ化チタンの存在を示す特異イオンとしては,m/z=76,104がよい.3)今回選定した特異イオンを用いて窒化ケイ素と金属との接合界面を分析した結果,反応生成物層が二層構造になっているというこれまでの分析電子顕微鏡及び,X線光電子分光法による分析結果が確認できた.

A Solid electrolyte interphase (SEI) that is formed on both anode and cathode surfaces during the early charge process, plays an important role stabilizing lithium ion battery (LiB) operation, by preventing further electrolyte decomposition during charge and discharge. Generally, electrolyte additives are used in order to effectively stabilize SEIs. Lithium bis-oxalato borate (LiBOB) is one example of such an effective additive that forms stable SEI on electrodes to inhibit the degradation of the graphite anode, improving the capacity retention during the cycling test at high temperature. Detailed mechanism on the impact of LiBOB additive, however, remains unknown. We, therefore, analyzed the SEI of graphite negative electrode with and without LiBOB by using Hard X-ray photoelectron spectroscopy (HAX-PES) which is suitable to analyze over-all structure of deposited SEIs with deep probing length. In addition, we performed NMR to confirm chemical composition of D2O-extracted components of SEIs. An electrolyte that consists of standard 1 M LiPF6 salt dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate (EC / DEC) in a 3:7 volume ratio was used. 3 wt% of LiBOB additive (Sigma-Aldrich Co. LLC) was added into the electrolyte. The coin-type cell, which is composed of a cathode electrode LiNi1/3Co1/3Mn1/3O2, a graphite anode and polyethylene separator, were assembled with different electrolytes in an argon-filled glove box. Charge-discharge tests were repeated for 50 cycles in the potential rage of 3.0-4.2 V at 50 °C at a charge/discharge rate of 1C. Then, the cell was disassembled and the anode was retrieved, and repeatedly washed with DEC in an argon-filled glove box. The HAXPES measurements were carried out at the BL46XU beamline at SPring-8. Figure shows C 1s HAXPES spectra for the graphite anodes after 1st and 50th charge and discharge cycles. The spectra were fitted with six peaks centered at 282.2eV (Peak 1), 284.2 eV (Peak 2), 285.6eV (Peak3), 287.9 eV (Peak 4), 289.2 eV (Peak 5), 290.1 eV (Peak 6). Peak 1 can be assigned to graphite. Peak2 can be assigned to chemical components for lithium alkyl carbonate, the organic materials of SEI. Peak 5 can be associated with a carbonate component for the Li2CO3, the inorganic material of SEI. Peak 3 and Peak 6 include the hydrocarbon and organofluorine components for the PVdF binder. Peak4 can be assigned oxalate originate in LiBOB decomposition. First, we note that the graphite peak (P1) in the C 1s HAXPES was still observed spectra even after 50th charge and discharge cycles. This result indicates that the depth of HAXPES (hν = 8 keV) is larger than thickness of SEI, thus HAXPES detected whole SEI and a part of the active materials exists underneath SEI film in the depth direction. After 50th cycles, the peak intensity of P1 decreased and the increase with remarkable peak intensity of P5 was observed without LiBOB additive. This indicates that thickness of inorganic SEI on graphite anode without LiBOB additive is larger than that of SEI with LiBOB additive. The similar tends were observed for LiF and POx components on graphite (the F 1s and P 1sXPS spectra were not shown). More detailed mechanism will be discussed at the Meeting combined with NMR data. Figure 1

Introduction Establishment of lifetime prediction methodology for Li-ion batteries (LIBs) is strongly required in order to prolong the lifetime of LIBs and to use LIBs in safe. While “square root (SQRT) law” has been proposed to predict the lifetime of LIBs based on the growth mechanism of solid electrolyte interphases (SEIs) [1], the SQRT law cannot describe the degradation behavior precisely in whole period of LIB operation, especially near the end stage of degradation, because the detailed mechanism of degradation remains unknown. We, therefore, investigated the detailed structure of SEIs in heavily deteriorated anodes by Hard X-ray photoelectron spectroscopy (HAXPES) technique [2] that enables us to investigate the chemical composition of the whole SEIs in non-destructive way, and then, we discuss the reason of deviation from the SQRT law. Experimental A commercial 18650-type LIB cell, which consists of a graphite anode, Li(Ni1/3Mn1/3Co1/3)O2 cathode, and LiPF6 in a mixture solvent of EC, PC, EMC and DMC as electrolyte, was used in this study. Cells were charged and discharged with 1C rate (0, 100, 200 and 500cycles) at 25ºC. The cells were then disassembled in an argon glove box, in which the oxygen and water contents were maintained below 1 ppm. Then the electrodes were washed with highly purified DMC to remove the residual electrolyte components. After washing, the electrodes were vacuum-dried to evaporate the solvents and then transferred to the analysis chamber by using a transfer vessel. The HAXPES measurements were carried out at the BL46XU beamline at SPring-8. The photon energy of incident X-rays was 14 keV. The X-ray take-off angle was 80º Results and discussion Figure 1(a) shows the change of discharge capacity retention as a function of SQRT of the number of charge/discharge cycle. Although discharge capacity retention was proportional to SQRT up to 300cycles, a sudden reduction was observed around 300 cycles. We show the pictures of disassembled anodes after cycle tests in Fig. 1(b). We observed the inhomogeneous degradation in anode sheet especially on 500 cycled. At the outside, the surface of the anode layer was discolored to blue, and at the inside, we observed the depositions. We, then, investigated the distribution of SEI growth on the anode sheet in addition to the cycle dependence of SEI growth. Figures 1(c) and (d) show C 1s spectra obtained by using 14 keV HAXPES. We can easily find the graphite peak (283.9 eV) was observed in all samples by using 14 keV HAXPES. In XPS spectra with Al Kα incident X-rays (hv = 1486.6eV), this graphite peak wasn’t observed in almost all samples. This indicates that the probing depth of 14 keV HAXPES is larger than thickness of SEI, thus 14 keV HAXPES detected whole SEI and a part of the graphite exists underneath SEI formed on all the anodes in the depth direction. In order to look the difference in cycle dependence of SEI growth between the outside and inside of an anode sheet, we focused on the intensity of graphite peak. In Fig. 1(c), we observed that the intensity of graphite peak gradually decreases with increasing cycles. This indicates that the SEI gradually grew with increasing cycles at the outside. On the other hand, in Fig. 1(d), sudden decrease in the intensity of graphite peak was observed on 500 cycled, though the intensity of graphite peak hardly changes on 100 and 200 cycled. This result suggests that SEI dramatically grew between 200 and 500 cycles at the inside. This behavior coincides with the sudden reduction of discharge capacity retention. From these results, one reason for the sudden reduction of discharge capacity retention was considered to be caused by the irreversible loss of Li due to rapid SEI growth at the inside of anode sheet. At the meeting, we will also discuss about the variation of the chemical composition of SEI and the factor of rapid SEI growth. Acknowledgement The synchrotron experiments were carried out on beamline BL46XU at SPring-8 with approvals from Japan synchrotron radiation institute (JASRI) (Proposal No. 2014B1903). Reference [1] H. Yoshida et al ., Electrochemistry 71, 1018 (2003). [2] M. Matsumoto et al,. 226thECS meeting A5-422. Figure caption Fig.1 (a) Cycle dependence of discharge capacity retention. (b) Pictures of disassembled anodes after cycle tests. (c) and (d) C 1s spectra obtained by using 14 keV HAXPES at the outside and at the inside of an anode sheet, respectively. Figure 1

This paper describes the development and the characterization of a Li+ optical sensor (optode) based on a Li+ selective fluoroionophore (KBL-01-Si), immobilized to a mesoporous silica thin film. KBL-01-Si was synthesized by the formation of a urethane bond between the hydroxyl terminated alkoxy chain of KBL-01 and 3-isocyanatopropyl-triethoxysilane. Li+ optodes with different amounts of KBL-01-Si fluoroionophore were fabricated by changing the grafting time of KBL-01-Si to mesoporous silica thin films with two different pore sizes. When the concentration of KBL-01-Si immobilized to the pore surface of the mesoporous silica thin films was low, response curves following a theoretical 1 : 1 complex formation equilibrium with binding constants for Li+ (log K) between 4.38 and 5.04 were observed. At higher concentrations of immobilized fluoroionophore, the response curves deviated from the fitting curve based on a theoretical chemical equilibrium, and the dynamic response was extended over a broad range from 10−6 to 1 M. In addition, it was observed by XPS depth profiling that KBL-01-Si was mainly localized on pore surface areas close to the channel entrances. These results indicate that not only the design of the fluoroionophore, but also the matrix for immobilization, and the microscale distribution of the fluoroionophore affect the characteristics of an ion sensor.

An investigation was made of the reasons why ferroelectric PbTiO3 films are hard to grow on single-crystal Si substrates. PbTiO3 films were formed on Si(100) and MgO(100) single-crystal substrates, and X-ray photoelectron spectroscopy (XPS) was used to analyze the composition, chemical structure and oxidation state at the interface between the substrate and the film. It was found that lead, oxygen and silicon diffused markedly at the interface and that the PbTiO3 film experienced both a lead deficiency and Si diffusion. These phenomena are thought to be the reasons why it is difficult to form good PbTiO3 films on silicon substrates by chemical vapor deposition (CVD). It was observed that the addition of TiO2 and ZrO2 films at the interface with the silicon substrate reduced the diffusion of Si to the PbTiO3 film.

Raman scattering spectra of 3C-SiC films, grown heteroepitaxially on Si(111) substrates by chemical vapor deposition (CVD), were measured to obtain information on the relaxation mechanism of the internal stress of the 3C-SiC films. The internal stress is found to be relaxed by the formation of the voids at the interface between 3C-SiC film and Si substrate during the CVD process.

Surface analysis of the ceramic-steel interface joined with an active metal and brazing metal foils was carried out by SEM, TEM, EDX and XPS. The analyzed specimen was the sintered silicon nitride joined to SNCM steel by Ti metal and Ag/Cu (72/28) brazing metal.(1) Two reaction layers were produced between Si3N4 and braze.(2) A reaction layer facing Si3N4 (layer I) was about 300nm thick and composed mainly of titanium nitride (TiN).(3) The other reaction layer (layer II) between layer I and the braze was composed of titanium nitride (TiN) and silicide (Ti5Si3). The thickness of this layer was about 3μm.

The relation between the mechanical properties and the microstructure of an air-annealed 20-vol% SiC-whisker/Y-TZP composite was examined. Although the bend strength and fracture toughness were 950 MPa and 8.2 MPa {center dot}m{sup 1/2}, respectively, before this composite was air-annealed, after annealing both properties decreased. Fracture was more intergranular than transgranular after aging because of microcracking caused by the t {yields} m transformation and cavity formation at the grain boundary during aging.

Surface analysis of the joining interface between silicon nitride (Si3N4) and metal with an active metal foil was carried out by XPS, SEM-EDX to make clear joining mechanism and action of brazing metals. The reaction product layer of the specimen which contained brazing metal was constituted two layers, and was about 5μm thick. Layer I facing Si3N4 was composed of titanium nitride (TiN), and layer II facing brazing metals was composed of TiN and titanium silicide (Ti5Si3). The reaction product layer of a specimen without brazing metal was about 0.4μm thick and composed of TiN, Ti5Si3 and elemental silicon (Si). On the basis of the data obtained by this analysis, it was considered that;(a) During the initial stage of joining, Si3N4 reacts with titanium at the interface to produce TiN and Si according to reaction (1).Si3N4+4Ti→4TiN+3Si (1)(b) At a system contained brazing metals, diffusion of Si into the inside was accelerated to react with non-reacted Ti and from Ti5Si3 according to reaction (2).3Si+5Ti→Ti5Si3 (2)(c) Action of brazing metals accelerates the diffusions of Si, TiN, Ti5Si3 and Ti, and products wide reaction layer.

X線光電子分光分析法(XPS)を用いたポリ塩化ビニル(塩ビ)の表面劣化状況を分析する手法を検討した.測定手法としてCls, Cl2p, Olsの各ピーク面積から炭素量を基準にした塩酸量や酸化量の定量分析を行い塩ビ表面の劣化状況を解析した.塩ビは可塑剤などの添加剤を含んでおり,表面にはこの添加剤の層が存在するため,XPS分析を行う以前に試料中の添加剤を抽出により取り除く必要がある.抽出溶媒,抽出時間を検討した結果,ジエチルエーテルがヘキサンやエタノールに比べて良好な結果が得られることが分かった.又,抽出時間は4時間以上必要であり,8時間に設定した.ジエチルエーテル抽出後の試料表面は酸素濃度が深さ方向に大きく変化しておりこれを更に水で16時間抽出することにより安定な定量値が得られた.水抽出を行った場合,相対標準偏差6%で塩素量を,13%で酸素量を測定することが可能であることが確認できた.この手法を用いて熱劣化試料の分析を行った結果,塩ビの表面劣化は脱塩酸反応と酸化反応が同時に起こっていることが推定された.又,Clsピークをピーク分離することにより,カルボニル基やカルボキシル基が生成することも確認できた.

SIMSを用いて窒化ケイ素と金属との接合界面の元素及び生成物の深さ方向分布分析及び三次元分布分析を行い,以下の知見を得た.(1)窒化ケイ素と金属との接合界面に存在する反応生成物層が二層構造になっているという,これまでの分析電子顕微鏡及びX線光電子分光分析結果が確認できた.(2)ろう材成分の一つである銀が接合界面付近にも微量ではあるが含まれていることが新たに分かった.(3)反応生成物であるケイ化チタン濃度の平面方向の位置による差は深さ方向の差に比べて少ないことが分かった.

Features of modulated structures in Bi{sub 2}Sr{sub 2}Ca{sub 1{minus}{ital x}}Y{sub {ital x}}Cu{sub 2}O{sub {ital y}} have been investigated by means of electron microscopy. In addition to two one-dimensional modulated structures with different periods, a new structure modulated along the {ital a} and {ital b} axes is found in 0.8{le}{ital x}{le}1.0. A high-resolution electron micrograph shows that the new structure is characterized by the periodic array of wavy stripes along the {ital b} axis.

Wear behavior of silicon nitride (Si3N4) ceramic tools in turning gray cast iron was evaluated. Wear of the flank and rake faces decreased with increasing cutting speed in a range of 100 to 300m/min. Deposits on the rake and flank faces after cutting 3.3km were analyzed by electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). When the cutting speed was 300m/min, surface deposits consisting of Mn, S, Al, and O were detected by EPMA. In contrast, little Al and O were found on the tool surface at a cutting speed of 100m/min. Similar results were obtained for the flank face by EPMA. The rake face of the tool after cutting at 300m/min was analyzed in detail by XPS. It was determined that the main contents of the surface deposits were Al2O3 and silicon oxide (SiO2 and SiOx); the layer was 1 to 2μm in thickness. It was revealed that the oxide deposits prevented direct contact between silicon nitride cutting tool and the workpiece. This worked to improve tool life when turning of gray cast iron at a high cutting speed.