Diffusion of p-aminoazobenzene in SBS block copolymer

The temperature dependence of p-aminoazobenzene diffusion in a styrene–butadiene–styrene (SBS) triblock copolymer film, prepared from a toluene or ethyl acetate solution, was investigated in the temperature region from 40° to 110°C by using a sublimative desorption method. Parallel studies on the mechanical relaxations of this copolymer were carried out in the same temperature range to be compared with the diffusion data. The penetrant-diffusion characteristics were interpreted in terms of Fujita's free-volume theory with due consideration of the different SBS domain morphology. The value of B_d, defined as the diffusional volume ratio of a penetrant molecule to a segment, was then estimated as 0.45–0.55 above the T_g of the polystyrene phase or 0.7 below that temperature. Interestingly, sigmoidal desorption appeared in the range under the T_g of the polystyrene phase for film cast from ethyl acetate; the anomalous behavior was considered to reflect the slow relaxation process of the copolymer chain ascribable to the predominant exposure of the polystyrene phase on the film surface.     

Dispersion of carbon nanotubes in ethanol by a bead milling process

Carbon nanotubes (CNTs) were dispersed in ethanol by bead milling to form a CNT suspension. The size and shape of the CNTs were not changed after bead milling. The Brownian motion of the CNTs was observed by an optical microscope. It was shown by analysis off the trajectory of individual CNTs that the diffusion coefficient of their translational Brownian motion was 4.5 × 10⁻¹³ m² s⁻¹. The ratio of the particle mobilities due to drift flow and diffusion flow was 2.4, which is almost the same as for a high-molecular-weight protein. Shear thinning occurred in the CNT suspension, which means that the CNTs were oriented in the suspension under a high shear rate at low viscosity. The intrinsic viscosity for shear rates of 0 and ∞ agreed with those calculated using Simha’s equation and Leal and Hinch’s equation, respectively. Based on the experimental results, the CNTs were found to be well dispersed as isolated and nanosized rod-like particles in the suspension. CNT-dispersed Si₃N₄ ceramics were fabricated using the CNT suspensions. As a result, the bead milling improved the bend strength of the CNT Si₃N₄ ceramics compared with the wet ball milling because granules of CNTs were eliminated by the bead milling.     

Swelling behavior of crosslinked hydroxypropylcellulose films retaining cholesteric liquid crystalline order,II. Effects of temperature,solvent, and pH

Crosslinked hydroxypropylcellulose (HPC) films were cast from the cholesteric liquid crystalline HPC solution in methanol. The films retained the cholesteric liquid crystalline order. The dependences of swelling behavior of our films in water and propanol on temperature and on pH of the solvent were determined. The response of our films to the changes in water, temperature and in pH was discussed. In water, the equilibrium swelling ratio (B_e) decreased with temperature whereas B_e increased with temperature in propanol. For a given composition of water and propanol, B_e was independent of temperature. B_e in the acidic solvents was higher than in the alkaline solvents. The response data to the stepwise change in temperature revealed that the deswelling behavior was more rapid than the swelling behavior in water, and the swelling-deswelling behavior was reversible. The response to the stepwise change in pH was almost the same as that of the change in temperature, but the surface of the film was attacked by the acid and became fluffy with increasing soaking time.     

Curing of epoxy resin contaminated with water

Epoxy resins used for reinforcement of bridges and buildings are explored in the light of both curing rates and mechanical properties when resins are contaminated with water in outdoor construction. The developed resin is composed of a conventional resin of bisphenol A diglycidyl ether and a hardener with a polyoxipropyldiamine base. Curing rates were obtained by time variation of the near infrared absorbance of amine groups in the hardener at various water contents. They obeyed the second‐order reaction law with respect to the hardener, of which the activation energy was 70 kJ mol⁻¹. Water increased the reaction rate. Mechanical properties such as ultimate tensile strength, adhesive shear stress, and flexural strength were measured at various water contents for the developed epoxy resin and the commercially available low‐temperature epoxy resin. The developed cured resin shows not only higher mechanical strengths but also much less deterioration by water than the conventional cured resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 214–220, 2001     

Separation of aqueous phenol through polyurethane membranes by pervaporation. II. Influence of diisocyanate and diol compounds and crosslinker

The influence of diisocyanate and diol compounds of polyurethane and crosslinking agent on the separation of phenol aqueous solution by pervaporation was investigated. Polyurethanes were prepared by polyaddition of diisocyanate and diol compounds and trimethylolpropane (TMP) using dibutyltindilaulate as a catalyst. The polyurethane membrane was prepared by a casting method and was sandwiched with a porous polypropylene membrane (Celgard® 2500). Pervaporation measurement was carried out under vacuum on the permeate side, and the permeant was collected with a liquid nitrogen trap. Little influence of diisocyanate compounds on the phenol permselectivity through diisocyanate–polytetramethyleneglycol [PTMG(1000)] membranes was observed since the influence on the solubility and the diffusivity was small. The phenol permselectivity was increased with an increase in the molecular weight of PTMG and polycaprolactone diol (PCL) for the 1,6‐diisocyanato hexane (HMDI)–PTMG and HMDI–PCL membranes. It was considered that the increase in phenol diffusivity can be attributed to an increase in phenol selectivity. The permeability and selectivity of HMDI–[PTMG(2900)–TMP] membrane was relatively constant below the 2% TMP content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 439–448, 1999     

Discrete-time advanced PID control systems for unknown time delay systems and their applications

PID control schemes have been used widely in most process control systems represented by chemical processes for a long time. Indeed, they are easy for most engineers in many industries to understand and for the use of various systems, whose properties are obscure. However, conventional PID control schemes have not been so available for the systems whose system parameters and time delays are unknown. The purpose of this paper is to consider advanced PID control schemes in discrete-time systems with unknown time delays. Two control schemes, that is, compound PID control systems with a local feedback compensator and a pre-compensator are proposed, and they are extended to explicit-type self-tuning PID control schemes. Furthermore, these methods are applied to a pressure-control system to show their effectiveness. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 118 (3): 50–57, 1997     

Design of advanced integral-type marine reactor, MRX

The basic concept of an innovative advanced marine reactor with a passive safety system, MRX (Marine Reactor X) has been established for the primary application to ship propulsion. The design goals of the reactor system, to be lightweight and compact, and to be enhanced in safety and reliability, are achieved with adoption of new technologies. The MRX is of the integral-type PWR with 100 MW of thermal output. Adoption of a water-filled containment makes the MRX extremely lightweight and compact. The total weight and volume of MRX is about 1600 tons and 1210 m³, which is half that of the first Japanese nuclear ship, ‘Mutsu’, reactor, although the reactor power of MRX is three times greater than that of the ‘Mutsu’ reactor. Numbers of active components in the reactor system are greatly reduced, compared with loop type PWRs, by adopting an integral type reactor and the passive system. Safety was evaluated by both experiments and analyses. Core damage occurrence frequency estimated by probability safety analysis (PSA) is of two orders smaller than those of existing PWRs. Feasibility study on economics is conducted by comparing the total operation costs of a nuclear container ship installing the MRXs with a diesel engine ship. The nuclear ship has the advantage for greater speed and larger amounts of cargo carried.     

A new class of transparent polymeric materials. I. Production and properties of an alternating copolymer of N-methylmaleimide and isobutene

An alternating copolymer of N-methylmaleimide and isobutene was produced by a radical precipitation polymerization method. The copolymer thus produced is a new class of transparent polymeric material that shows a unique balance of optical, thermal, and mechanical properties. The visible light transmittance was more than 90% and the stress optical coefficient was smaller than that of polycarbonate, leading to moldings with lower birefringence. The heat deflection temperature of the copolymer was as high as 157°C, and the thermal expansion coefficient was about 30% smaller than those of poly(methyl methacrylate) and polycarbonate. The copolymer showed excellent mechanical properties, specifically, the flexural modulus was the highest among the typical amorphous polymers. © 1996 John Wiley & Sons, Inc.     

In Situ PD-L1 Expression in Oral Squamous Cell Carcinoma Is Induced by Heterogeneous Mechanisms among Patients

The expression of programmed death ligand-1 (PD-L1) is controlled by complex mechanisms. The elucidation of the molecular mechanisms of PD-L1 expression is important for the exploration of new insights into PD-1 blockade therapy. Detailed mechanisms of the in situ expression of PD-L1 in tissues of oral squamous cell carcinomas (OSCCs) have not yet been clarified. We examined the mechanisms of PD-L1 expression focusing on the phosphorylation of downstream molecules of epidermal growth factor (EGF) and interferon gamma (IFN-γ) signaling in vitro and in vivo by immunoblotting and multi-fluorescence immunohistochemistry (MF-IHC), respectively. The in vitro experiments demonstrated that PD-L1 expression in OSCC cell lines is upregulated by EGF via the EGF receptor (EGFR)/PI3K/AKT pathway, the EGFR/STAT1 pathway, and the EGFR/MEK/ERK pathway, and by IFN-γ via the JAK2/STAT1 pathway. MF-IHC demonstrated that STAT1 and EGFR phosphorylation was frequently shown in PD-L1-positive cases and STAT1 phosphorylation was correlated with lymphocyte infiltration and EGFR phosphorylation. Moreover, the phosphorylation pattern of the related molecules in PD-L1-positive cells differed among the cases investigated. These findings indicate that PD-L1 expression mechanisms differ depending on the tissue environment and suggest that the examination of the tissue environment and molecular alterations of cancer cells affecting PD-L1 expression make it necessary for each patient to choose the appropriate combination drugs for PD-1 blockade cancer treatment.     

Influence of Delayed Harvest Time on Physico‐chemical Properties of Sweetpotato Starch

Eight varieties of sweetpotato [Ipomoea batatas (L.) Lam] were transplanted in June, and harvested in October, November, December 1999 and January 2000. Starch content and starch properties of the tuberous roots were compared on delaying the harvest date. The shoot tops got blighted in early December and chilling injury rate of roots (average of eight varieties) increased up to 76.7% in January with decrease in temperature. Starch contents in October (24.0 g/100 g fresh weight, fw) and November (25.0 g/100 g fw) were almost the same, but the content decreased remarkably in December (21.2 g/100 g fw) and January (15.5 g/100 g fw). In December and January, the sucrose content of the roots had higher values. Hardness and leaked water percentage (LWP) of the starch gels remarkably increased from November to December (hardness: 76.4 to 112.3 g, LWP: 6.6 to 10.9%). On the contrary, the changes in amylose content and pasting properties of the starches were not consistent with decrease in temperature. This suggests that the effect of low temperature on these properties is insignificant after the growth period of sweetpotato. There were significant differences among the varieties in terms of starch retrogradation. The selection of varieties such as Kyushu 123 with the lowest percentage of retrogradation and Kyukei90142‐8 with the lowest chilling injury rate will help to lengthen the storage time in the field at least until December.