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.

     

Differential Scanning Calorimetric Study of Solidification Behavior of Monoacylglycerols to Investigate the Cold-Flow Properties of Biodiesel

Monoacylglycerols (MAG) are impurities present in biodiesel as a result of incomplete reactions. MAG often solidify in biodiesel even at room temperature because of their high melting points. This worsens the cold-flow properties such as the cloud point and pour point. We hypothesized that several types of MAG solidify simultaneously; therefore, we performed differential scanning calorimetry of binary mixtures of MAG to elucidate their interactions during solidification. Three thermodynamic formulas were then applied to the experimental results: (1) non-solid-solution, (2) solid-solution, and (3) compound formation models. Binary mixtures of MAG showed complicated liquidus curves with multiple upward convex shapes, with which only the compound formation model fitted well. This model was applied to multicomponent mixtures that consisted of MAG and fatty acid methyl esters (FAME) as surrogate biodiesel fuels. We confirmed that the model still worked well. The results show that the compound formation model has good potential for predicting the cold-flow properties of biodiesel.     

Single-particle-diagnosis approach: An efficient strategy for discovering new nitride phosphors

Discovery of novel phosphors is extremely important to target the ever change of the solid state lighting technology. In this paper, we present a high-speed way to discover new phosphors, namely single-particle-diagnosis approach. This approach is based on investigating the crystal structure and luminescence of a tiny single crystal, without the necessity of the growth of large-size single crystals or the preparation of single phase powder samples. The concept of the approach and some new nitride phosphors explored by this approach are shown in this paper.     

Control of Oxidation State of Eu Ions in Na2O–Al2O3–SiO2 Glasses

Glasses doped with well‐controlled Eu³⁺ and Eu²⁺ ions have attracted considerable interest due to the possibility of tuning the wavelength range of the emitted light from violet to red by using their ⁵D₀→⁷F_j and 5d–4f electron transitions. Glasses were prepared to dope Eu³⁺ ions in a Na₂O–Al₂O₃–SiO₂ system, and the changes in the valence state of Eu³⁺ ions and the glass structure surrounding the Eu atoms during heating under H₂ atmosphere were investigated using fluorescence spectroscopy, X‐ray absorption fine‐structure spectroscopy, and ²⁷Al magic‐angle spinning solid‐state nuclear magnetic resonance spectroscopy. The reduction behavior of Eu³⁺ ions was dependent on the Al/Na molar ratio of the glass. For Al/Na < 1, the Al³⁺ ions formed the AlO₄ network structure accompanied by the Na⁺ ions as charge compensators; the Eu³⁺ ions occupied the interstitial positions in the SiO₄ network structure and were not reduced even under heating in H₂ gas. On the other hand, in the glasses containing Al₂O₃ with the Al/Na ratio exceeding unity, the Eu³⁺ ions commenced to be coordinated by the AlO₄ units in addition to the SiO₄ network structure. When heated in H₂ gas, H₂ gas molecules reacted with the AlO₄ units surrounding Eu³⁺ ions to form AlO₆ units terminated with OH bonds, and reduced Eu³⁺ ions to Eu²⁺ via the extracted electrons.     

Forgetting curve of cricket,Gryllus bimaculatus,derived by using serotonin hypothesis

It is thought that the adjustment of intraspecific aggression is an essential factor in the development of a social structure. To understand the natural laws for organizing the social structure, we focus on the fighting behavior of crickets, Gryllus bimaculatus, and investigate the neuronal mechanisms to adjust aggressiveness associated with a neuromodulatory biological amine: serotonin (5-HT).In this paper, we present a working theory of a neurophysiological mechanism based on the past biological studies on the 5-HT hypothesis, and a mathematical model of the mechanism. We analyzed this model and concluded that this neurophysiological mechanism makes the forgetting process slower. Next, we fitted our theoretical forgetting curve to an experimental curve and estimated the parameters of our model. These estimated values were in agreement with common belief in biological science.     

A monolithically integrated high‐efficiency Cu(In,Ga)Se2 mini‐module structured solely by laser

Monolithically integrated Cu(In,Ga)Se₂ mini‐modules were fabricated in order to reduce the width of patterning related dead area. The Cu(In,Ga)Se₂ layers were prepared on soda‐lime glasses using the multistage process at low substrate temperature below 500 °C. A picosecond laser with a wavelength of 532 nm was used for all of the structuring processes (P1, P2, and P3) for the monolithic integration. A “lift‐off” type structuring was applied for P1 and P3, and an “ablation” type was for P2. The laser structuring was optimized to be minimizing the dead area width, and the width of about 70 µm was successfully achieved. A mini‐module, in which the optimized structuring processes were applied for the integration, demonstrated a certified efficiency of 16.6%. Copyright © 2015 John Wiley & Sons, Ltd.     

Fundamental welding R&D results for manufacturing vacuum vessel of JT-60SA

The real vacuum vessel (VV) manufacturing of JT-60SA has started since November 2009 at Toshiba. Prior to starting manufacturing, fundamental welding R&Ds had been performed by three stages. In the first stage, primary tests for screening welding method were performed. In the second stage, the trial welding for 1 m-long straight and curved double shell samples were conducted. The dependences of welding quality and distortion on the welding conditions, such as arc voltage and current, setting accuracy, welding sequence, and the shape of grooves were studied. In addition, welding condition with low heat input was explored. In the last stage, fabrication sequence was confirmed and established by the trial manufacturing of the 20° upper half mock-up [1]. This paper presents the R&D results obtained in the first and second stages.