Chemically assisted laser ablation ICP mass spectrometry

A new laser ablation technique combined with a chemical evaporation reaction has been developed for elemental ratio analysis of solid samples using an inductively coupled plasma mass spectrometer (ICPMS). Using a chemically assisted laser ablation (CIA) technique developed in this study, analytical repeatability of the elemental ratio measurement was successively improved. To evaluate the reliability of the CLA-ICPMS technique, Pb/U isotopic ratios were determined for zircon samples that have previously been analyzed by other techniques. Conventional laser ablation for Pb/U shows a serious elemental fractionation during ablation mainly due to the large difference in elemental volatility between Pb and U. In the case of Pb/U ratio measurement, a Freon R-134a gas (1,1,1,2-tetrafluoroethane) was introduced into the laser cell as a fluorination reactant. The Freon gas introduced into the laser cell reacts with the ablated sample U, and refractory U compounds are converted to a volatile U fluoride compound (UF6) under the high-temperature condition at the ablation site. This avoids the redeposition of U around the ablation pits. Although not all the U is reacted with Freon, formation of volatile UF compounds improves the transmission efficiency of U. Typical precision of the 206Pb/238U ratio measurement is 3-5% (2sigma) for NIST SRM 610 and Nancy 91500 zircon standard, and the U-Pb age data obtained here show good agreement within analytical uncertainties with the previously reported values. Since the observed Pb/U ratio for solid samples is relatively insensitive to laser power and ablation time, optimization of ablation conditions or acquisition parameters no longer needs to be performed on a sample-to-sample basis.     

The Effect of the Oxygen Exchange at Electrodes on the High-Voltage Electrocoloration of Fe-Doped SrTiO3 Single Crystals: A Combined SIMS and Microelectrode Impedance Study

The effect of the electrode material on the high voltage stoichiometry-polarization (electrocoloration) of Fe-doped SrTiO₃ single crystals has been studied. For different electrode materials (150-nm Ag/15-nm Cr and 150-nm Au/15-nm Cr) secondary ion mass spectrometry (SIMS) was used to measure the depth profile of the ¹⁸O-isotope after high-field stress. The results were compared with spatially resolved impedance measurements on electrocolored Fe-doped SrTiO₃ single crystals. For Au/Cr as well as Ag/Cr electrodes a large dc voltage leads to moving color fronts which are usually correlated with a pronounced stoichiometry polarization of the samples due to electrodes blocking the ionic current. However, the local impedance measurements demonstrate that the conductivity profiles near the cathode depend on the electrode material. This finding is in accordance with the SIMS measurements which indicate that the Ag/Cr-electrodes are, in contrast to Au/Cr-electrodes not completely inactive for the oxygen incorporation into the Fe-doped SrTiO₃. The results are discussed in terms of defect chemical models.     

Structure and Bonding in Some Gd（Ⅲ） Metal Complexes Studied by Three-Dimensional X-Ray Analysis and ^155Gd Mossbauer Spectroscopy

Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd（Ⅲ） acetylacetonato complexes, Gd（pta）3 · 2H2O （pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione） and Gd（bfa）3 · 2H2O （bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione） were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd（pta）3 · 2H2O crystallizes in the P 2 1/n （#14） monoclinic space group and its lattice parameters are a = 1.4141（6） nm, b = 1.0708（3） nm, c =2.2344（4） nm, β =952.4（2）°, and Gd（bfa）3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 （1） nm, b = 2.295 （1） nm, c = 1. 0786（8） nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift （δ） of various Gd（Ⅲ） metal complexes having a different coordination number （C.N.） and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd（Ⅲ） metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.     

Temperature measurement at flip chip solder joint during electromigration test

Measuring the real temperature of a flip chip solder joint during an electromigration test has been a problem because of its small size and the local Joule heating due to a large applied current. A unique method that employs the electrical resistance change in the junction line between two solder joints was introduced to determine the temperature of the solder joint. The change in resistance was converted into temperature using a thermal coefficient of resistance of the junction line. The method accurately measured temperatures of the solder joint within 2 K until the solder joint resistance change ratio reached 100% due to growth of an electromigration void.     

TEM,XPS and SIMS Analyzes on Grain Boundary of Lanthanum Chromites

The morphological characteristics, chromium valence state, and cation transport in the vicinity of grain boundary in La_1-xCa_xCrO₃ were investigated by using TEM/EDS, XPS and SIMS techniques. The width of grain boundary was around 1 nm where anomalous enrichment of calcium was observed. Higher valence state of chromium such as Cr⁶⁺(d⁰) was detected in the grain boundaries whereas Cr³⁺(d³) and Cr⁴⁺(d²) were dominant in the bulk. Very fast interdiffusion of alkaline earths was observed in the Sr²⁺-La_0.75Ca_0.25CrO₃ system. All observed phenomena were correlated by assuming the A-site vacancy which may be induced by the formation of Cr⁶⁺ at grain boundaries.     

Reduction of return current noise by energy‐compensating active control

A newly proposed energy‐compensating active control is implemented to reduce the return current noise which is caused by inverter‐driven electric car systems. The energy‐compensating active control detects the energy charged at the filter capacitor, and reduces the energy and current of the noise frequency component by simple feedback loop incorporated with the conventional motor torque controller. No additional sensors or circuit arrangements are necessary; therefore, the return current can be attenuated effectively without any further cost. The return current with an inverter system is measured using a current probe and an FFT analyzer, and it is shown that the 25‐Hz noise current is reduced by up to 10 dB with the control. The results reveal that the low‐frequency return current noise can be attenuated with the simple control scheme, which would expectedly reduce the size of filter reactors and capacitors to meet the current limit level of the signaling system's track relays. © 2008 Wiley Periodicals, Inc. Electr Eng Jpn, 165(4): 84–91, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20615     

A brainlike learning system with supervised,unsupervised, and reinforcement learning

According to Hebb's cell assembly theory, the brain has the capability of function localization. On the other hand, it is suggested that in the brain there are three different learning paradigms: supervised, unsupervised, and reinforcement learning, which are related deeply to the three parts of brain: cerebellum, cerebral cortex, and basal ganglia, respectively. Inspired by the above knowledge of the brain in this paper we present a brainlike learning system consisting of three parts: supervised learning (SL) part, unsupervised learning (UL) part, and reinforcement learning (RL) part. The SL part is a main part learning input–output mapping; the UL part is a competitive network dividing input space into subspaces and realizes the capability of function localization by controlling firing strength of neurons in the SL part based on input patterns; the RL part is a reinforcement learning scheme, which optimizes system performance by adjusting the parameters in the UL part. Numerical simulations have been carried out and the simulation results confirm the effectiveness of the proposed brainlike learning system. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 162(1): 32–39, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20600     

Effect of geometry and dielectric material on thermo-mechanical strain on micro-vias in build-up substrates

Build-up substrates have been preferable solutions for small and high performance systems for more than a few decades. Micro-vias need to be smaller to realize ever higher wiring density in build-up substrates, but there has been concern on the reliability. This paper focuses on Cu filled micro-vias of 25 μm in diameter and investigates the strain on micro-vias using a finite element method for varying geometric parameters and material properties. The strain becomes smaller with shrinking micro-vias, and a prediction equation for the strain is developed as a function of the aspect ratio and material properties for both single and stacked micro-vias.     

Environmental stress cracking of poly(acrylonitrile-butadiene-styrene)

The environmental stress cracking (ESC) of acrylonitrile-butadiene-styrene (ABS) copolymer caused by a non-ionic surfactant (poly-oxyethylene alkylether) was studied by constant-load tensile creep tests and edge crack tension (ECT) tests. The fracture surfaces were investigated by a scanning electron microscope (SEM) and the morphology of the crack tip was investigated by a transmission electron microscope (TEM). It was found that the results of the creep tests performed in the non-ionic surfactant were very different from those performed in air. SEM images of the fracture surfaces showed that there were three different mechanisms of fracture and that specimens had a tendency to rupture by ESC when the stress was small. The results of the ECT tests and the TEM images showed that the change in the mechanism of the fracture was attributable to the change of morphology at the crack tip.     

Relationship between Expression of Onco-Related miRNAs and the Endoscopic Appearance of Colorectal Tumors

Accumulating data indicates that certain microRNAs (miRNAs or miRs) are differently expressed in samples of tumors and paired non-tumorous samples taken from the same patients with colorectal tumors. We examined the expression of onco-related miRNAs in 131 sporadic exophytic adenomas or early cancers and in 52 sporadic flat elevated adenomas or early cancers to clarify the relationship between the expression of the miRNAs and the endoscopic morphological appearance of the colorectal tumors. The expression levels of miR-143, -145, and -34a were significantly reduced in most of the exophytic tumors compared with those in the flat elevated ones. In type 2 cancers, the miRNA expression profile was very similar to that of the exophytic tumors. The expression levels of miR-7 and -21 were significantly up-regulated in some flat elevated adenomas compared with those in exophytic adenomas. In contrast, in most of the miR-143 and -145 down-regulated cases of the adenoma-carcinoma sequence and in some of the de novo types of carcinoma, the up-regulation of oncogenic miR-7 and/or -21 contributed to the triggering mechanism leading to the carcinogenetic process. These findings indicated that the expression of onco-related miRNA was associated with the morphological appearance of colorectal tumors.