Correlation between gas transport properties and the morphology/dynamics of crystalline fluorinated copolymer membranes

The crystalline structure, dynamics, and gas transport properties (i.e., the gas permeability, gas diffusion coefficient, and gas solubility coefficient) of poly(tetrafluoroethylene‐co‐perfluoroethylvinylether) (PFA) membranes were systematically investigated via differential scanning calorimetry, wide/small/ultra‐small‐angle X‐ray scattering, and quasielastic neutron scattering measurements. We evaluated the gas transport properties using a constant‐volume/variable‐pressure method. The gas permeability and the gas diffusion coefficient decreased with increasing crystallinity of the PFA membranes at crystallinities below 32%. However, in membranes with a crystallinity of 32% or greater, these parameters depended on the characteristics of the gas molecules, such as their kinetic diameter. The so‐called long spacing period and the thickness of the crystalline/amorphous regions increased with crystallinity according to the small/ultra‐small‐angle X‐ray scattering results. Furthermore, the quasielastic neutron scattering measurements indicated that the scattering law was well fitted to a sum of narrow and broad Lorentzian components. In particular, the narrow components, that is, the local motion of amorphous components and side chains, increased with crystallinity. These results suggest that large gas molecules could pass through the PFA membranes, assisted by the motion in the amorphous region. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45665.     

Effect of glass transition temperature on heat‐responsive gas bubbles formation from polymers containing tert‐butoxycarbonyl moiety

Various types of polymers containing tert‐butoxycarbonyl (BOC) moiety as the typical protecting group of functional moieties have been used for the design of stimuli‐responsive polymer materials. In this study, we investigated the heat‐responsive deprotection behavior of BOC‐containing polymers obtained by radical polymerization of 4‐(tert‐butoxycarbonyloxy)styrene (BSt) and copolymerizations of BSt with styrene and methyl acrylate. The deprotection of BOC groups accompanying the evolution of isobutene and carbon dioxide as gaseous products was monitored by thermogravimetric analyses at different temperature circumstances; that is, on heating at a rate of 10 °C/min and under isothermal conditions at various temperatures. The deprotection resulted in a significant decrease in the transmittance of visible light due to the formation of a large number of gas bubbles, that is, foaming, in the polymer films when a heating temperature was close to the glass transition temperature of the used polymer. The potential of BOC‐containing polymers was also evaluated as the heat‐responsive adhesive polymers for dismantlable adhesion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46252.     

DNA Computing Boosted by a Cationic Copolymer

The huge information storage capability of DNA and its ability to self‐assemble can be harnessed to enable massively parallel computing in a small space. DNA‐based logic gates are designed that rely on DNA strand displacement reactions; however, computation is slow due to time‐consuming DNA reassembly processes and prone to failure as DNA is susceptible to degradation by nucleases and under certain solution conditions. Here, it is shown that the presence of a cationic copolymer boosts the speed of DNA logic gate operations that involve multiple and parallel strand displacement reactions. Two kinds of DNA molecular operations, one based on a translator gate and one on a seesaw gate, are successfully enhanced by the copolymer without tuning of computing conditions or DNA sequences. The copolymer markedly reduces operation times from hours to minutes. Moreover, the copolymer enhances nuclease resistance.     

Experimental study of the Mode I adhesive fracture energy in DCB specimens bonded with a polyurethane adhesive

The Mode I fracture energy of a polyurethane adhesive with low Young’s modulus was investigated. Metal adherends in standardized double cantilever beam (DCB) tests are typically too stiff for soft adhesives, making it difficult to measure the fracture energy accurately. However, soft adhesives, such as a single-component polyurethane adhesive tested in this paper, are in high demand in the automobile industry. Thus, accurate measurement techniques must be established. Flexible substrates composed of spring steel were used for the DCB tests to accommodate the deformation of the adhesive layer. First, the applicability of the flexible substrates was discussed using specimens bonded with an epoxy adhesive. For soft adhesives, however, the deformation of the adhesive layer must be considered in the calculation methods of the fracture energy. Although the deformation effect on the DCB tests has been discussed with Winkler’s elastic foundation, the crack length must be measured along with the load and displacement. To overcome the difficulty of measuring the crack length, a calculation method based on Winkler’s elastic foundation was introduced applying the compliance-based beam method (CBBM). Finally, the fracture energy of the polyurethane adhesive was discussed by comparing the calculation methods with and without measuring the crack length.     

Photoelectric properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with polyhedral oligomeric silsesquioxane

4,4′‐(Hexafluoro‐isopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) was synthesized and reacted with polyhedral oligomeric silsesquioxane (POSS) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The solid‐state and optical properties of the resulting copolymers were systematically investigated, and their electronic states were analyzed. As the POSS concentration increased, the transparency across the entire wavelength range increased. In the ABA‐type triblock copolymers, a new transition was observed between the highest occupied molecular orbital in POSS and the lowest unoccupied molecular orbital in 6FDA‐TeMPD because of their high molecular size dispersion. Since the refractive index of 6FDA‐TeMPD decreased linearly as the POSS concentration increased, the refractive index of the ABA‐type triblock copolymers of 6FDA‐TeMPD with POSS could be easily controlled. POLYM. ENG. SCI., 57:1207–1213, 2017. © 2017 Society of Plastics Engineers     

Electrochemical reaction engineering of polymer electrolyte fuel cell

Although fuel cells can be considered as a type of reactor, methods of kinetic analysis and reactor modeling from the viewpoint of chemical reaction engineering have not yet been established. The rate of an electrochemical reaction is a function of concentration, temperature, and interfacial potential difference (or electromotive force). This study examined the cathode reaction in a polymer electrolyte fuel cell, in which oxygen and protons react over platinum in the catalyst layer (CL). The effects of the oxygen partial pressure and the cathode electromotive force on the reaction rate were assessed. Resistance to proton transport increases the electromotive force and reducing the reaction rate. It was established that the effectiveness factor of the cathode CL is determined by competition between the reaction and mass transport of oxygen and protons. Two dimensionless moduli that govern the cathode behavior are proposed as a means of depicting the processes in the cell. © 2016 American Institute of Chemical Engineers AIChE J, 63: 249–256, 2017     

Spectroscopic and Photoluminescent Properties of Indium Zinc Oxide (IZO) and IZO/Ag/IZO Sandwiched Film

We report the ellipsometric and photoluminescence (PL) properties of Indium zinc oxide (IZO) films, which were grown by radio frequency sputtering under Ar and O₂ atmospheres. IZO films grown under an O₂ atmosphere (IZO (O₂)) showed enhanced PL properties when compared to the films grown under an Ar atmosphere (IZO (Ar)), particularly with respect to the band-edge emission. The enhancement of band-edge emission can be attributed to the reduction in the non-emissive defect states related to oxygen vacancies, which were repaired by sputtering under O₂ atmosphere, whereas the PL enhancement in green region is probably due to the formation of the different types of defects under the excess oxygen environment. This was also supported by the results of time-resolved PL measurements, where the band-edge emission of IZO (Ar) showed rapid decay with a 50 ps lifetime, which indicates the dominance of the relaxation pathway to underlying defect states. In contrast, the PL decay profiles of IZO (O₂) for band-edge and emissive defect states showed moderate decay with time-constants of 2.3 ns and 5.7 ns, respectively. The exciton relaxation dynamics were sensitive to the presence and its kinds of defect states, which were controlled by the growth conditions.     

Methanogenic digestion using mixed substrate of acetic, propionic and butyric acids

Experiments on methanogenic digestion using high concentrations of mixed substrate were conducted. The major intermediate products of anaerobic digestion such as acetic, propionic and butyric acids were mixed in a ratio of 2:1:1 (COD basis), respectively, and used as a substrate for feeding into continuous-flow chemostat reactors maintained at 35°C. These reactors were operated stably at higher feed substrate concentrations and shorter hydraulic retention times (HRT) than those of using a single component of volatile fatty acids as a substrate. At an HRT of 4.43 days, the methanogenesis occurred normally up to a feed substrate concentration of 70,000 mg COD I⁻¹. At a feed substrate concentration of 20,000 mg COD I⁻¹, the methanogenesis occurred normally up to an HRT of 2.91 days and the minimum SRT for microbial populations was calculated to be 2.42 days. An increase in feed substrate concentration adversely affected the propionate degradation strikingly, while a decrease in HRT significantly adversely affected the acetate and propionate degradation. The methane production was 0.301 g⁻¹ COD utilized, and it was independent of the feed substrate concentration and HRT. Bacilli were predominant in all reactors, but sarcinae appeared in the reactors with high feed substrate concentrations and short HRTs. Phenomena in digester failure due to methanogen washout were also observed.     

Multiple evaluations of the removal of pollutants in road runoff by soil infiltration

Groundwater replenishment by infiltration of road runoff is expected to be a promising option for ensuring a sustainable urban water cycle. In this study, we performed a soil infiltration column test using artificial road runoff equivalent to approximately 11-12 years of rainfall to evaluate the removal of pollutants by using various chemical analyses and bioassay tests. These results indicated that soil infiltration treatment works effectively to remove most of the pollutants such as organic matter (chemical oxygen demand (CODMn) and dissolved organic carbon (DOC)), P species, polycyclic aromatic hydrocarbons (PAHs), numerous heavy metals and oestrogenic activities. Bioassay tests, including algal growth inhibition test, Microtox and mutagen formation potential (MFP) test, also revealed effective removal of toxicities by the soils. However, limited amounts of NO3, Mn, Ni, alkaline earth metals, perfluorooctane sulphonate (PFOS) and perfluorooctane sulphonamide (FOSA) were removed by the soils and they possibly reach the groundwater and cause contamination.     

A pattern recognition technique for structural identification using observed vibration signals: Nonlinear case studies

A novel pattern recognition technique, support vector regression (SVR), has been introduced for linear structural parameter identification in a companion article. It is recognized that structural systems in general are designed to behave nonlinearly when subjected to extreme loading. Therefore SVR-based methods for nonlinear structural identification (SI) have been studied and they are summarized in this paper. The first method uses the SVR technique to identify nonlinear structural parameters, whereby the power parameter controlling the shape of the Bouc–Wen model is known. The second and third methods conduct nonlinear SI in the power parameter unknown condition, with the difference that the third method adopts a model selection strategy to enhance the nonlinear parameter estimation practicability. Five-story nonlinear structural systems whose restoring forces are expressed by the Bouc–Wen model are investigated to demonstrate the effectiveness of the SVR-based SI methods. Verification results show that the third method using the model selection strategy is the most efficient one for nonlinear structural parameter identification.