Radical polymerization of butyl acrylate and random copolymerization of styrene and butyl acrylate and styrene and methyl methacrylate mediated by monospiro- and dispiropiperidinyl-N-oxyl radicals

Radical polymerization of butyl acrylate (BA) and random copolymerizations of styrene (St) and BA and St and methyl methacrylate (MMA) in the presence of 7-aza-15-hydroxydispiro[5.1.5.3]hexadecane-7-yloxyl (1) and 1-aza-2,2-dimethyl-4-hydroxyspiro[5.6]dodecane-1-yloxyl (2) were carried out. Radical polymerization of BA at 120 °C in the presence of 1 gave poly(BA) with M_n=20200 and M_w/M_n=1.30 at 23% conversion. The termination of polymerization observed around ∼20% conversion was solved to a certain extent by an addition of small amounts of dicumyl peroxide, and poly(BA) with M_n=37400 and M_w/M_n=1.33 was obtained in 46% yield. Random copolymerizations of St and BA and St and MMA in the presence of 1 and 2 at 80 °C gave the corresponding random copolymers with narrow polydispersities of 1.12-1.38 at the molar fraction above 0.30 of St in feed. The kinetic study for the NO-C bond homolysis of the corresponding alkoxyamines prepared from 1 and 2 were carried out, and evaluation of the preexponential factors (A_act) and the activation parameters (E_act) showed that the steric factors of the nitroxides are reflected mainly on E_act.     

Preparation and characterization of electroplated amorphous gold-nickel alloy film for electrical contact applications

A process for electroplating amorphous gold-nickel alloy with the atomic ratio of unity was developed. The plating bath was prepared by adding potassium cyanoaurate(I) into a known plating bath which produces amorphous nickel-tungsten alloy. At a sufficiently high gold concentration, the alloy deposit did not contain any tungsten. The amorphous nature of the Au-Ni alloy produced in the new bath was confirmed by using TEM and THEED. Hardness, resistivity, and contact resistance of this new alloy were determined, and the results are discussed for applications as an electrical contact material.     

Design and Fabrication of a Novel Electrode-Supported Honeycomb SOFC

We report the design and fabrication of a novel electrode-supported honeycomb solid oxide fuel cell (SOFC), that can generate high volumetric power density. Among various cell designs, honeycomb SOFCs are suitable for compact SOFC modules because they have a large surface electrode area per unit volume. We have succeeded in fabricating a cathode-supported honeycomb SOFC via extrusion of a LaSrMnO₃ honeycomb monolith and through the use of a new slurry injection method for the channel surface coating using electrolyte/anode bi-layers. The fabricated honeycomb SOFCs exhibited high volumetric power densities of approximately 1.2 W/cm³ at 600°C under a wet H₂ fuel flow.     

Pervaporation via silicon-based membranes: Correlation and prediction of performance in pervaporation and gas permeation

Pervaporation (PV) is a membrane technology that holds great promise for industrial applications. To better understand the PV mechanism, PV dehydrations of various types of organic solvents (methanol, ethanol, iso-propanol, tert-butanol, and acetone) were performed on five types of organosilica and two types of silicon carbide-based membranes, all with different pore sizes. Water permeance was dependent on the types of organic aqueous solutions, which suggested that organic solvents penetrated the pores and hindered the permeation of water. In addition, water permeance of various types of membranes in PV was well correlated with hydrogen permeance in single-gas permeation. Furthermore, a clear correlation was obtained between the permeance ratio in PV and that in single-gas permeation, which was confirmed via the modified-gas translation model. These correlations make it possible to use single-gas permeation properties to predict PV performance.     

Mixing in multiple-impeller stirred tank reactors with boiling liquids

Mixing in a boil-off mechanically stirred tank reactor with multiple impellers was examined. Power consumption and gas hold-up were measured in boiling water in a 0.2 m i.d. stirred tank reactor with three four-pitched blade downflow disk turbines. Vapour was generated from both the immersed ring heater and the impellers. At low vapour generation rates, vapour was mainly generated from the impellers rather than from the heater, whereas nucleation occurred at the heater instead of the impeller at higher vapour generation rates. The mechanical power consumption decreased due to vapour generation. The change in boiling-to-non-boiling mechanical power ratio with varying impeller rotational speed and boiling rate was complicated and not monotonous except at higher impeller speeds and boiling rates. The gas hold-ups increased with increasing vapour generation rate but were rather small as compared to those in cold gas dispersing systems. Empirical correlations for power consumption and gas hold-up in boiling liquids were developed using the present experimental data.     

Atomic bonds in boron carbon nitride films synthesized by remote plasma-assisted chemical vapor deposition

Boron carbon nitride (BCN) films are synthesized by remote plasma-assisted chemical vapor deposition (RPCVD) method. The present experimental apparatus is featured by introducing BCl₃ gas near the substrate without mixing to plasma consisting of N₂ and CH₄ gases. Two sample groups of the BCN films are prepared. One is grown with various CH₄ flow rates, and another is grown with various BCl₃ flow rates. The composition ratio of the constituent atoms, atomic bonds and optical bandgap are investigated. C composition ratio of the BCN film increases with increasing CH₄ flow rate, leading to a reduction in the optical bandgap with increasing C composition ratio. On the other hand, it is found that no significant variation in the composition ratio occurs for the BCN films grown with various BCl₃ flow rates and that the optical bandgap decreases with increasing BCl₃ flow rate. This behavior of the optical bandgap is related to a change of the atomic bonds in the BCN film grown with various BCl₃ flow rates.     

Abscopal Effect of Frozen Autograft Reconstruction Combined with an Immune Checkpoint Inhibitor Analyzed Using a Metastatic Bone Tumor Model

We evaluated the abscopal effect of re-implantation of liquid nitrogen-treated tumor-bearing bone grafts and the synergistic effect of anti-PD-1 (programmed death-1) therapy using a bone metastasis model, created by injecting MMT-060562 cells into the bilateral tibiae of 6–8-week-old female C3H mice. After 2 weeks, the lateral tumors were treated by excision, cryotreatment using liquid nitrogen, excision with anti-PD-1 treatment, and cryotreatment with anti-PD-1 treatment. Anti-mouse PD-1 4H2 was injected on days 1, 6, 12, and 18 post-treatment. The mice were euthanized after 3 weeks; the abscopal effect was evaluated by focusing on growth inhibition of the abscopal tumor. The re-implantation of frozen autografts significantly inhibited the growth of the remaining abscopal tumors. However, a more potent abscopal effect was observed in the anti-PD-1 antibody group. The number of CD8+ T cells infiltrating the abscopal tumor and tumor-specific interferon-γ (IFN-γ)-producing spleen cells increased in the liquid nitrogen-treated group compared with those in the excision group, with no significant difference. The number was significantly higher in the anti-PD-1 antibody-treated group than in the non-treated group. Overall, re-implantation of tumor-bearing frozen autograft has an abscopal effect on abscopal tumor growth, although re-implantation of liquid nitrogen-treated bone grafts did not induce a strong T-cell response or tumor-suppressive effect.     

Construction of a robot control system which understands a voice and pointing actions

This research was aimed at making a robot that can go and get an object designated by the user. We produced a robot control system that uses pointing and voice control. This control system is composed of two systems. One system is the object instruction system that uses pointing, and the other is the object instruction system that uses voice. The approximate position of a designated object is recognized by the object instruction system that uses pointing, and information about the object and instructions about the operation are conveyed by the object instruction system that uses voice. This time, the object instruction system that uses pointing has been designed and verified as the first step. A calculation resource to calculate the approximate position of the designated object is obtained when the user points directly at the object. A robot can be moved around a designated object by using this system. The object instruction system that uses voice will be constructed in future work.