Local structure,glass transition,structural relaxation,and crystallization of functional oxide glasses investigated by Mössbauer spectroscopy and DTA

This review paper summarizes early Mössbauer and DTA studies of different oxide glasses containing small amounts of iron (III) or tin (IV) as the probe. A lot of valuable information of the atomic level has been obtained about the role of nonbridging oxygen (NBO), network former (NWF), network modifier (NWM), local network structure, glass transition, structural relaxation, crystallization, etc. Introduction of alkali oxide into iron (III)-containing oxide glass causes a marked decrease in glass transition temperature (T_g) amounting to 100 °C and a concordant decrease in quadrupole splitting (Δ) of Fe^III, which reflects decreased distortion of NWF–oxygen polyhedra and formation of NBO. By contrast, introduction of non-alkali oxide into oxide glass causes an increase in T_g amounting to more than 100 °C and a concordant increase in Δ, reflecting increased distortion of NWF–oxygen polyhedra in highly cross-linked network. These experimental results led to a discovery of “T_g-Δ rule”, which was consistent with the “conformer model” proposed for polymers by Matsuoka and Quan. Debye temperatures (θ_D) obtained by low-temperature Mössbauer measurements proved to be useful to determine short- and long-range structures of glass and glass ceramics. Isothermal annealing of vanadate glasses at temperatures higher than T_g or crystallization temperature (T_c) causes a “tunable” decrease in DC-resistivity from the order of MΩ cm to Ω cm. Introduction of metal oxide with a narrow bandgap (E_g) is highly effective to increase the conductivity after the annealing. It was proved that “structural relaxation” of NWF–oxygen polyhedra and resultant decrease in the activation energy (E_a) for conduction are responsible for the improved conductivity. Heat treatment of IR-transmitting aluminate, gallate, and tellurite glasses at temperatures higher than T_g or T_c revealed that crystallization was triggered by the cleavage of NWF–oxygen bonds. These findings will contribute to the development of functional glass and glass ceramics such as smart glass and eco-friendly glass.

     

Combinatorial Measurement of CDKN1A/p21 and KIF20A Expression for Discrimination of DNA Damage-Induced Clastogenicity

In vitro mammalian cytogenetic tests detect chromosomal aberrations and are used for testing the genotoxicity of compounds. This study aimed to identify a supportive genomic biomarker could minimize the risk of misjudgments and aid appropriate decision making in genotoxicity testing. Human lymphoblastoid TK6 cells were treated with each of six DNA damage-inducing genotoxins (clastogens) or two genotoxins that do not cause DNA damage. Cells were exposed to each compound for 4 h, and gene expression was comprehensively examined using Affymetrix U133A microarrays. Toxicogenomic analysis revealed characteristic alterations in the expression of genes included in cyclin-dependent kinase inhibitor 1A (CDKN1A/p21)-centered network. The majority of genes included in this network were upregulated on treatment with DNA damage-inducing clastogens. The network, however, also included kinesin family member 20A (KIF20A) downregulated by treatment with all the DNA damage-inducing clastogens. Downregulation of KIF20A expression was successfully confirmed using additional DNA damage-inducing clastogens. Our analysis also demonstrated that nucleic acid constituents falsely downregulated the expression of KIF20A, possibly via p16 activation, independently of the CDKN1A signaling pathway. Our results indicate the potential of KIF20A as a supportive biomarker for clastogenicity judgment and possible mechanisms involved in KIF20A downregulation in DNA damage and non-DNA damage signaling networks.     

Development of function-graded proton exchange membrane for PEFC using heavy ion beam irradiation

The graded energy deposition of heavy ion beam irradiation to polymeric materials was utilized to synthesize a novel proton exchange membrane (PEM) with the graded density of sulfonic acid groups toward the thickness direction. Stacked Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were irradiated by Xe⁵⁴⁺ ion beam with the energy of 6 MeV/u under a vacuum condition. The induced trapped radicals by the irradiation were measured by electron spin resonance (ESR) spectroscopy. Irradiated films were grafted with styrene monomer and then sulfonated. X-ray photo-electron spectroscopy (XPS) spectra showed that the densities of sulfonic acid groups were controlled for injection “Surface” and transmit “Back” sides of the fabricated PEM. The membrane electrode assembly (MEA) fabricated by the function-graded PEM showed improved fuel cell performance in terms of voltage stability. It was expected that the function-graded PEM could control the graded concentration of sulfonic acid groups in PEM.     

A chemo-thermo-mechanically coupled analysis of ground deformation induced by gas hydrate dissociation

We present a numerical analysis of gas hydrate dissociation in hydrate-bearing sediments in the seabed ground. Behavior of multiphase materials has been described within the framework of a macroscopic continuum approach through the use of the theory of porous media. The proposed simulation method has been developed based on chemo-thermo-mechanically coupled analysis, taking into account phase changes from solids to fluids, that is, water and gas, flow of water and gas, heat transfer, and ground deformation. From the numerical results, it has been found that ground deformation is induced by generation and dissipation of water and gas, and by reduction of soil strength due to the loss of hydrates.     

Investigation of localized deformation in partially saturated sand under triaxial compression using microfocus X-ray CT with digital image correlation

In this paper, localized deformation in partially saturated sand was investigated quantitatively using microfocus X-ray computed tomography (CT) and an image analysis of the CT images. Triaxial compression tests on a partially saturated dense Toyoura sand specimen were carried out under a low confining pressure and under drained conditions for both air and water. The development of localized deformation was observed macroscopically using microfocus X-ray CT, and the displacement field over the entire specimen was quantified by an image analysis of the CT images with the digital image correlation (DIC) technique. The progressive development of shear bands is discussed with reference to these images. In addition, the region of localization was observed microscopically by partial CT scanning on a micron scale with high spatial resolution. Changes in the particulate structures are also discussed herein. The DIC image analysis of the partial CT images provided a microscopic displacement field and indicated that very fine localized shear deformation developed before the shear bands had become visible in the macroscopic investigation.     

Immunomodulatory effect of mushrooms on cytotoxic activity and cytokine production of intestinal lamina propria leukocytes does not necessarily depend on β-glucan contents

We evaluated the effects of seven mushroom extracts (Grifola frondosa, Pholiota nameko, Panellus serotinus, Hypsizygus marmoreus, Pleurotus cornucopiae, Armillaria mellea, and Flammulina velutipes) on cytotoxic activity and cytokine production of lamina propria leukocytes (LPLs) isolated from rat small (S) and large (L) intestinal mucosa. Boiling water extracts from seven species of mushrooms showed no direct cytotoxicity against the YAC-1 target cells. However, prominent increases of cytotoxicity were observed in S- and L-LPLs co-cultured with P. serotinus extract. Cytokine production (TNFα, IFNγ, IL-12 p70, and IL-4) of S- and L-LPLs was stimulated in response to P. cornucopiae extract. Mushroom extracts contributed to target cell adhesion and/or cytokine production in the effector cells. The promotion of cytotoxic activity in S- and L-LPLs was not necessarily related to β-glucan content of the mushroom.     

Spin Dynamics in ZnO-Based Materials

In this work, we address the issue of spin relaxation and its relevance to spin detection in ZnO-based materials, by spin-polarized, time-resolved magneto-optical spectroscopy. We have found that spin relaxation is very fast, i.e. about 100 ps for donor bound excitons in wurtzite ZnO, despite of a weak spin–orbit interaction. We also reveal that alloying of ZnO with Cd enhances spin relaxation, prohibiting ZnCdO/ZnO structures for efficient optical spin detection. On the other hand, a variation in strain field induced by lattice mismatch with substrates does not seem to lead to a noticeable change in spin relaxation. The observed fast spin relaxation, together with the limitation imposed by the band structure, are thus identified as the two most important factors that limit the efficiency of optical spin detection in the studied ZnO-based materials.     

Numerical simulation on void bubble dynamics using moving particle semi-implicit method

In present study, the collapse of void bubble in liquid has been simulated using moving particle semi-implicit (MPS) code. The liquid is described using moving particles and the bubble–liquid interface was set to be vacuum pressure boundary without interfacial heat mass transfer. The topological shape of bubble can be traced according to the motion and location of interfacial particles. The time dependent bubble diameter, interfacial velocity and bubble collapse time were obtained under wide parametric range. The comparison with Rayleigh and Zababakhin's prediction showed a good agreement which validates the applicability and accuracy on MPS method in solving present momentum problems. The potential void induced water hammer pressure pulse was also evaluated which is instructive for further material erosion study. The bubble collapse with non-condensable gas has been further simulated and the rebound phenomenon was successfully captured which is similar with vapor-filled cavitation phenomenon. The present study exhibits some fundamental characteristics of void bubble hydrodynamics and it is also expected to be instructive for further applications of MPS method to complicated bubble dynamics problems.     

Numerical computation of thermally controlled steam bubble condensation using Moving Particle Semi-implicit (MPS) method

In the present study, single steam bubble condensation behaviors in subcooled water have been simulated using Moving Particle Semi-implicit (MPS) method. The liquid phase was modeled using moving particles and the two phase interface was set to be a movable boundary which can be tracked by the topological position of the interfacial particles. The interfacial heat transfer was determined according to the heat conduction through the interfacial liquid layer and the coupling between momentum and energy was specially treated. Computational results showed that the bubble experiences various deformations at lower degrees of liquid subcooling while it remains nearly spherical at higher degrees of liquid subcooling. The bubble lifetime is nearly proportional to bubble size and is prolonged at higher system pressures. Bubble lifetime obtained from the MPS method agrees well with the experiments of 10 and 11, however it is lower than the predictions of Sudhoff et al. (1982). The underestimation is caused by severe bubble deformation at lower degrees of subcooling. The present study exhibits some fundamental characteristics of single steam bubble condensation and is expected to be instructive for further applications of the MPS method to evaluate more complicated bubble dynamics problems.