Practical Continuous‐Flow Controlled/Living Anionic Polymerization

A continuous‐flow reaction system was developed, allowing flow conditions of the entire system to be maintained at a predetermined constant level, which is one of the most significant factors for successful industrial application. Controlled/living anionic polymerization was selected as a model reaction since the characteristics of its polymer products, molecular weights, and molecular weight distributions are highly susceptible to changes in the relative flow rates of a monomer and initiator solutions. In flow microreactors, controlled/living anionic polymerization of styrene in tetrahydrofuran (THF)/hexane initiated by THF‐diluted n‐butyllithium (n‐BuLi) was examined. Poly(styrenes) of larger molecule sizes such as Mn > 15 000 were successfully synthesized. After continuous operation for four hours, ca. 0.5 kg of the polymer was readily produced with narrow molecular weight distribution, demonstrating the applicability of this continuous‐flow system for controlled/living anionic polymerization on considerably large scale with a view to its industrial usage in the future.     

Effect of addition of corrosion inhibitors on corrosion behaviors of PCV material under diluted artificial seawater environment

ABSTRACT

Fukushima Daiichi nuclear power plants (1F) were damaged by unprecedented severe accident in the great east Japan earthquake, and seawater and freshwater had been injected as an emergency countermeasure for the core cooling. Although, the primary containment vessel (PCV) was not supposed to be exposed to diluted seawater, the PCV will be exposed to diluted seawater environment until fuel debris removal is completed. Therefore, it is necessary to establish a countermeasure of corrosion for the PCVs made of carbon steel. In this study, the effect of the addition of corrosion inhibitor, which is one of the corrosion countermeasures, was investigated by two types of corrosion tests. As a result of the immersion corrosion test, it was found that any of the three kinds of corrosion inhibitor could suppress corrosion of carbon steel. In addition, as a result of the inhibitor interim addition test, it was found that corrosion of carbon steel covered with corrosion products could be suppressed by optimizing the additive amount of corrosion inhibitor in the cooling water.     

Stabilizing effect of the cyclodextrins additive to spray-dried particles of curcumin/polyvinylpyrrolidone on the supersaturated state of curcumin

Although curcumin is considered to have various therapeutic effects, its use as a functional food or supplement is restricted owing to its low water solubility and bioavailability. To increase the solubility of curcumin in water, the use of polyvinylpyrrolidone (PVP) and vinylpyrrolidone-vinyl acetate copolymers with a pyrrolidone skeleton was noted to be promising. In particular, the bi-component formulations of curcumin/PVP prepared through spray drying exhibited an amorphous state in powder X-ray diffraction observations and temporally increased the apparent solubility of curcumin to over 5000 times that of untreated curcumin; nevertheless, after 24 h, the solubility decreased owing to the unstable supersaturated state of curcumin. The addition of α-cyclodextrin (α-CyD) in the bi-component curcumin/PVP formulation helped maintain the supersaturated state of curcumin, whereas the addition of β- and γ-CyD led to the collapse of the supersaturated state. The addition of α-CyD can likely help inhibit the nucleation and crystal growth of curcumin, through the interaction among the solubilized units of curcumin/PVP and α-CyD.     

Theoretical study of the temperature dependent hydrogen storage capacity of Pd and Ti nanoparticles

A hybrid simulation was carried out using discrete variational (DV) Xα molecular orbital and molecular dynamics methods to examine the storage of hydrogen in metal nanoparticles. The calculation load was light and therefore could be performed quickly on a generic personal computer. The simulation investigates the electronic states of hydrogen on Pd and Ti nanoparticles. The hydrogen dissociation behavior on the metal surface was reproduced, and the calculated bonding orbitals of Pd and hydrogen are consistent with other reports. The diffusion coefficient of hydrogen inside the metal displays the same temperature dependence as the theoretical results. This simplified calculation, which produces results in agreement with experimental/theoretical values, could lead to improved simulation methods for hydrogen storage materials.     

Effects of Thermal History and Microstructure on Segregation of Phosphorus and Alloying Elements in the Heat-Affected Zone of a Low Alloy Steel

The grain boundary segregation of phosphorus and alloying elements in the heat-affected zone (HAZ) of a low alloy steel was studied quantitatively with atom probe tomography. Non-equilibrium segregation mainly occurred during welding and subsequent fast cooling, leading to remarkable segregation of P, C, Mn, and Mo. The segregation of these four types of solutes showed similar microstructure-dependence at this stage, in which the segregation levels are higher in coarse-grained HAZ and intercritically reheated coarse-grained HAZ than in fine-grained HAZ. After simulated aging, P and Mn showed further enrichment at grain boundaries through equilibrium segregation, while desegregation was observed for C and Mo. In addition, it seems that precipitation of Mo at dislocations was greatly promoted during aging, which probably also contributed to the increase of P and Mn at grain boundaries.     

Evaluation of Young’s modulus of imprinted hydrogen silsesquioxane pillar after residual layer removal by reactive ion etching

Nanoimprint lithography has two basic steps. The first is the imprint step in which a mold with nanostructures on its surface is pressed into a resin film on a substrate, followed by removal of the mold. The second step is the residual layer removal by a reactive ion etching (RIE). There is no report whether the properties of the imprinted structure after RIE change or not. In this work, the authors evaluated the Young’s modulus of the imprinted pillar after residual layer removal by RIE. In this experiment, hydrogen silsesquioxane (HSQ), a type of spin-on-glass, was used as an imprint material. The residual layer was etched by RIE using CHF₃ gas. The Young’s modulus of imprinted pillar after RIE was measured via cantilever method. The Young’s modulus of HSQ pillar after RIE was twice as much as that of HSQ pillar before RIE. From the Fourier transform infrared measurement, it was founds the chemical structure of HSQ was changed by forming network structure due to heating by RIE plasma energy. These results indicate that the mechanical property of imprinted structure was changed in the residual layer removal step by using RIE.