Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Birth–death process of local structures in defect turbulence described by the one-dimensional complex Ginzburg–Landau equation

Defect turbulence described by the one-dimensional complex Ginzburg–Landau equation is investigated and analyzed via a birth–death process of the local structures composed of defects, holes, and modulated amplitude waves (MAWs). All the number statistics of each local structure, in its stationary state, are subjected to Poisson statistics. In addition, the probability density functions of interarrival times of defects, lifetimes of holes, and MAWs show the existence of long-memory and some characteristic time scales caused by zigzag motions of oscillating traveling holes. The corresponding stochastic process for these observations is fully described by a non-Markovian master equation.     

The effect of artifacts on dependence measurement in fMRI

The study of effective connectivity by means of neuroimaging depends on the measurement of similarity between activity patterns at different locations in the brain, without necessarily presupposing a particular model for this dependence. When these interactions are measured using functional magnetic resonance imaging (fMRI) techniques, however, imaging and physiological artifacts create patterns of dependence that may be unrelated to cortical activity. We demonstrate some of these effects through the measurement of short-range dependencies present in fMRI scans of the primary visual cortex (V1) in the anaesthetized macaque monkey. High-field (4.7 T) fMRI scans were conducted to measure responses based on the blood oxygen level-dependent contrast mechanism, during periods of no sensory stimulation and of visual stimulation with rotating polar-transformed checkerboard gratings. Dependence between the haemodynamic activity at different spatial locations (i.e., different voxels) was measured using correlation, mutual information and functional covariance. Particular attention was paid to understanding the sources of spurious dependence that may be observed during such investigations. Two main effects were detected: (a) short-range correlations introduced by the process of image reconstruction and (b) perturbations in the haemodynamic response caused by breathing. The image reconstruction artifacts were shown to create an artificially high short-range dependence in the readout direction of the scan, and the breathing artifacts caused enhanced short-range dependence in both the readout and phase-encode directions. Additional dependence in the phase-encode direction due to image-ghosting is also possible but will not be discussed in this report, as it can be alleviated by fine adjustment of preemphasis (elimination of eddy currents). A technique is described for removing breathing artifacts, and the effect of breathing on the apparent dependence between voxels is illustrated. The correlation of haemodynamic activity with the stimulus was found to be affected by breathing, although this effect can be neutralised by averaging the haemodynamic responses over many repetitions of the stimulus. Nonetheless, patterns of dependent activity between voxels may be lost in this averaging process, which makes the removal of breathing artifacts necessary if statistical dependence and the study of effective connectivity is the primary aim of an investigation.     

Influence of nanometer scale film structure of ZDDP tribofilm on Its mechanical properties: A computational chemistry study

We investigated the influence of a nanometer scale film structure of a tribofilm generated from zinc dialkyldithiophosphate (ZDDP) anti-wear additive on its mechanical properties using a combined molecular dynamics (MD) and finite element (FE) method. The frictional behavior of an interface between a native iron oxide layer on steel surface and zinc metaphosphate - regarded as a model material of ZDDP tribofilm - was firstly studied using the MD method. The results showed that the iron atoms in the oxide layer diffused into the phosphate layer during the friction process. The zinc atoms in the phosphate layer also diffused into the oxide layer. Significant interdiffusion of iron and zinc atoms was observed with increasing simulation time. Thus, metallic phosphate with a gradient composition of iron and zinc atoms was formed on the phosphate/oxide interface. We then constructed an axisymmetric nanoindentation simulation model from the MD-derived structures at a certain simulation time and carried out a FE calculation. As a result, we found that the rubbed ZDDP tribofilm, including the phosphate with the gradient composition of metallic atoms, showed larger contact stiffness and hardness. The combined MD/FE simulation indicates that the tribofilm becomes stiffer and harder due to the interdiffusion of iron and zinc atoms on the tribofilm/oxide interface. We have found that the gradient composition formation in ZDDP tribofilm during friction process influences on its mechanical properties.     

Preparation of Na+-selective electrodes by ion-implantation of lithium and silicon into single-crystal alumina wafer and its application to the production of ISFET

Summary Sodium ion-selective electrodes (Na⁺-ISE) were prepared by implanting Si⁺ and Li⁺ into alumina wafers and their characteristics were investigated. The alumina wafer had a thickness of 100 m and a diameter of 1.40 cm. The ionselective membrane was produced by ion-implanting of Li⁺ and Si⁺ on both sides of a single-crystal alumina wafer. The total doses of Li⁺ and Si⁺ were controlled to be the same, viz. 10¹³–10¹⁵ ions/cm². The ion-implanted alumina wafer with 10¹⁴ or 4×10¹⁴ ions/cm² of Li⁺ and Si⁺ showed better characteristics than the others.The response curves of the 10¹⁴ ions/cm² implanted alumina wafer had a slope of 42 mV/pNa in a concentration range from 1–10^–4mol/l. The full response achieved after about 1 min was reproducible. The proposed idea of producing Na⁺-ISE by ion-implantation technique was applied to functuate the gate surface of the field effect transitor to sodium ion. The sodium ion-sensitive FET (Na⁺-ISFET) prepared by implanting Li⁺ and Al⁺ at a dose of 5×10¹⁴ ions/cm² showed a slope of 30 mV/pNa in a concentration range from 1–10^–4mol/l.

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Herstellung Na⁺-ionenselektiver Elektroden durch Einbau von Lithium und Silicium in Einkristall-Alumniumoxidblättchen und Anwendung zur Erzeugung von ISFET

Zusammenfassung Na⁺-selektive Elektroden wurden durch Einbau von Si⁺ und Li⁺ in Aluminiumoxidblättchen hergestellt und ihre Charakteristiken untersucht. Die Blättchen hatten eine Dicke von 100 m und einen Durchmesser von 1,40 cm. Ebenso wurde die Membran für einen ISFET hergestellt. Die Gesamtmenge von Li⁺ und Si⁺ wurde auf 10¹³–10¹⁵ Ionen/cm² eingestellt, wobei sich bei 10¹⁴ oder 4×10¹⁴ Ionen/cm² die beste Charakteristik ergab.Die Responsekurven der mit 10¹⁴ Ionen/cm² versehenen Aluminiumoxidplättchen hatten eine Neigung von 42 mV/pNa in einem Konzentrationsbereich von 1–10^–4mol/l. Der nach 1 min erhaltene volle Response war reproduzierbar. Die vorgeschlagene Technik wurde zur Einstellung der Gate-Oberfläche des Feldeffekt-Transistors auf Natriumion benutzt. Der Na⁺-sensitive FET (Na⁺-ISFET), der durch Einbau von Li⁺ und Al⁺ mit 5×10¹⁴ Ionen/cm² hergestellt wurde, zeigte eine Neigung der Signalkurve von 30 mV/pNa in einem Bereich von 1–10^–4mol/l.

     

Determination of traces of ruthenium by neutron activation analysis using a polyethylene film

A neutron activation analytical method is described for the determination of traces of ruthenium. Acid solution of an inorganic chemical or seaweed ash is heated in a conical flask with oxidants, ruthenium ingredient is distilled and fixed on a polyethylene film, which is placed on the top of the flask. Many films were irradiated together in a thermal neutron flux, and after about a month γ-ray peak counts under the 497 keV peak of¹⁰³Ru were measured with a well-type NaI(Tl) or a Ge(Li) detector. In the chemicals of fifty one elements, compounds of four platinum metals were contaminated with 2100-150 ppb Ru, and Ga, In, Tm, Tb, Yb: all trivalent elements contained 510-16 ppb Ru. The ruthenium content of all other chemicals were of ppb order or less. In these, Ga, In, Tm and Yb were known as scintigram elements of cancer. In the ash of Porphyra tenera 2 ppb Ru was detected. A part of this work was done under the Visiting Researchers Program of Kyoto University Research Reactor Institute.