Zhao, Y.; Yoshimura, Kimio; Shishitani, Hideyuki*; Yamaguchi, Susumu*; Tanaka, Hirohisa*; Koizumi, Satoshi*; Szekely, N.*; Radulescu, A.*; Richter, D.*; Maekawa, Yasunari
Soft Matter, 12(5), p.1567 - 1578, 2016/02
Nuryanthi, N.*; Yamaki, Tetsuya; Kitamura, Akane; Koshikawa, Hiroshi; Yoshimura, Kimio; Sawada, Shinichi; Hasegawa, Shin; Asano, Masaharu; Maekawa, Yasunari; Suzuki, Akihiro*; et al.
Transactions of the Materials Research Society of Japan, 40(4), p.359 - 362, 2015/12
The ion-track grafting of a vinylbenzyl chloride (VBC) into a poly(ethylene-co-tetrafluoroethylene) (ETFE) film is necessary for preparing nanostructured hydroxide-ion-conductive electrolyte membranes. A key for success here is to obtain as high graft levels as possible (for higher conductivity) in a smaller number of tracks (for improving the other membrane properties). To this end, therefore, the effect of the medium for the VBC grafting was investigated as part of our continuing effort to optimize the experimental conditions. A 25 m-thick ETFE film was irradiated in a vacuum chamber with 560 MeV Xe at different fluences, and then the grafting was performed by immersing the irradiated films in a 20vol% VBC monomer at 60C. A medium was a mixture of water (HO) and isopropyl alcohol (iPrOH) at different volume ratios. The degree of grafting increased as the HO content became higher, and reached a maximum in pure HO. These results can be explained by considering the well-known Trommsdorff effect, in which poor solubility of the grafted polymer in polar media leads to an increased polymerization rate probably due to a lower termination rate.
Hamada, Takashi; Hasegawa, Shin; Fukasawa, Hideyuki*; Sawada, Shinichi; Koshikawa, Hiroshi; Miyashita, Atsumi; Maekawa, Yasunari
Journal of Materials Chemistry A, 3(42), p.20983 - 20991, 2015/11
no abstracts in English
Amemiya, Kuniaki*; Koshikawa, Hiroshi; Yamaki, Tetsuya; Maekawa, Yasunari; Shitomi, Hiroshi*; Numata, Takayuki*; Kinoshita, Kenichi*; Tanabe, Minoru*; Fukuda, Daiji*
Nuclear Instruments and Methods in Physics Research B, 356-357, p.154 - 159, 2015/08
Broadband low reflectance materials have various applications in the field of optical energy management; however, materials with ultra-low reflectance (below 0.1%) have been considered as mechanically delicate. We have developed a novel hard-surface optical absorber with microstructured, diamond-like carbon coated ion tracks on CR-39 plastic substrate. The spectral reflectance of the first prototype was below 2% for wavelengths ranging from 400 nm to 1400 nm; moreover, the optical absorber had mechanically hard surface and exhibited temporal durability. Choosing the appropriate design of the surface structure and coating layer is likely to reduce the reflectance to the order of 0.1%. This technique yields easy-to-handle broadband ultra-low reflectance absorbers.
Ooka, Makoto; Maekawa, Yasunari; Tomizuka, Chiaki; Murakami, Tomoyuki*; Katagiri, Genichi*; Ozaki, Hiroshi*; Kawamura, Hiroshi
JAEA-Technology 2015-003, 31 Pages, 2015/03
An action for the decommissioning of the Fukushima Daiichi Nuclear Power Station (Tokyo Electric Power Company) is pushed forward now. For fuel debris Remove, it is necessary to fill the Primary Containment Vessel (PCV) with water. Because a coolant leaks out from the PCV, it becomes the most important problem to seal leak the coolant. Nuclear Plant Decommissioning Safety Research Establishment has examined the method of seal leak using the photocoagulation resin. However, originally the photocoagulation resin is used as coating or the painting, and the applicability to seal leak water is unknown. This report describes the result that examined the applicability to seal leak using photocoagulation resin.
Yoshimura, Kimio; Koshikawa, Hiroshi; Yamaki, Tetsuya; Shishitani, Hideyuki*; Yamamoto, Kazuya*; Yamaguchi, Susumu*; Tanaka, Hirohisa*; Maekawa, Yasunari
Journal of the Electrochemical Society, 161(9), p.F889 - F893, 2014/06
Graft-type anion-conducting electrolyte membranes (AEMs) with imidazolium cations on graft polymers were synthesized through radiation-induced graft polymerization of -vinylimidazole (NVIm) on poly(ethylene-co-tetrafluoroethylene) (ETFE) films, followed by -propylation and ion-exchange reactions. The -propylation proceeded quantitatively, whereas the ion-exchange reactions in 1 M KOH at 60C were accompanied by partial -elimination of the imidazolium cations(AEM2), which exhibited an ion-exchange capacity (IEC) of 0.85 mmol g and ionic conductivity of 10 mS cm. AEM2 showed alkaline stability at 60C but it gradually degraded at 80C for ca. 150 h. The copolymer-type AEM (AEM3) with an IEC of 1.20 mmol g was prepared through the copolymerization of NVIm with styrene on ETFE films, followed by the same -propylation and ion-exchange reactions. AEM3 was shown higher alkaline durability in 1 M KOH at 80C. As a result, it exhibited higher conductivity (10 mS cm) for 250 h. Therefore, alkylimidazolium cations in copolymer grafts are a promising anion conducting group for alkaline-durable AEMs. A maximum power density of 75 mW cm is obtained for AEM3 in a direct hydrazine hydrate fuel cell.
Tran Duy, T.*; Sawada, Shinichi; Hasegawa, Shin; Yoshimura, Kimio; Oba, Yojiro*; Onuma, Masato*; Katsumura, Yosuke*; Maekawa, Yasunari
Macromolecules, 47(7), p.2373 - 2383, 2014/04
The hierarchical structures of graft-type ETFE-based polymer electrolyte membranes (ETFE-PEMs) were investigated using small- and ultrasmall-angle X-ray cattering experiments. The ETFE-PEMs with IECs 2.4 mmol/g possessed conducting graft domains around lamellar crystals, with a d-spacing of 21.8-29.1 nm, and oriented crystallites with short and long correlation distances of 218-320 and 903-1124 nm, respectively. The membranes with IECs 2.7 mmol/g showed a new phase of crystallite network domains with a d-range of 225-256 nm, indicating a phase transition from oriented crystallite to crystallite network structures in the IEC range of 2.4-2.7 mmol/g. Noted that for the ETFE-PEMs with high IECs higher conductivity at 30% RH and compatible tensile strengths at 100% RH and 80 C, compared with Nafion, originated from the well-interconnected ion channels around the crystallites and the remaining lamellar crystals and crystallites, respectively.
Chen, J.; Asano, Masaharu; Maekawa, Yasunari
Advanced Materials Research, 881-883, p.1157 - 1160, 2014/01
Cation and anion exchange membranes were prepared by radiation-induced graft polymerization of ethyl styrenesulfonate and chloromethyl styrene, respectively, onto poly(ethylene--tetrafluoroethylene) (ETFE) films, followed by hydrolysis in the former case and quaternization in the latter case. The degree of grafting as well as the ion exchange capacity (IEC) and the conductivity of the prepared membranes were investigated. Furthermore, the cation and anion exchange membranes were tested in an electrodialysis cell using caesium ion aqueous solution in the dilute compartment. It was found that the high-IEC membranes enhanced the electrodialysis speed, while the low-IEC membranes showed the high percent removal.
Tran, D. T.; Sawada, Shinichi; Hasegawa, Shin; Katsumura, Yosuke*; Maekawa, Yasunari
Journal of Membrane Science, 447, p.19 - 25, 2013/11
Relative humidity (RH) dependence of the proton conduction and mechanical properties of poly(ethylene-co-tetrafluoroethylene) (ETFE)-based radiation grafted polymer electrolyte membranes (PEMs) were investigated in a wide ion exchange capacity (IEC) range at 80 C. The proton conductivities of the ETFE-based PEMs for IECs of 1.3-2.9 mmol/g were 0.001-0.013 S/cm at 30% RH. These PEMs have conductivities that are less dependent on RH than aromatic-hydrocarbon-polymer based PEMs. The ETFE PEM (IEC 2.4 mmol/g) showed higher tensile strength than Nafion at 100% RH. It was revealed that the mechanical strength and proton conductivity were clearly related to PEM crystallinities.
Yamaki, Tetsuya; Nuryanthi, N.*; Koshikawa, Hiroshi; Asano, Masaharu; Sawada, Shinichi; Hakoda, Teruyuki; Maekawa, Yasunari; Voss, K.-O.*; Severin, D.*; Seidl, T.*; et al.
Nuclear Instruments and Methods in Physics Research B, 314, p.77 - 81, 2013/11
Ion-track membranes of poly(vinylidene fluoride) (PVDF), a type of fluoropolymer, could find wide applications due to its superior chemical and mechanical properties. In order to produce track-etched pores in PVDF films, we have independently employed much milder etching conditions without any oxidant additives in the alkaline etching solution. The goal of this work is to pursue the possibility of varying beam parameters and applying the effect of the etching pretreatment to control the pore size and shape. Ongoing in-situ/on-line analyses at the M-branch of the UNILAC would shed light on the detailed chemistry of not only ion-induced degradation but also the post-irradiation reactivity.
Nuryanthi, N.*; Yamaki, Tetsuya; Koshikawa, Hiroshi; Asano, Masaharu; Sawada, Shinichi; Hasegawa, Shin; Maekawa, Yasunari; Katsumura, Yosuke*
Nuclear Instruments and Methods in Physics Research B, 314, p.95 - 98, 2013/11
Our efforts have been focused on ion-track etched membranes of poly(vinylidene fluoride) (PVDF). This study deals with the effect of the transmembrane potential applied during the conductometry in order to offer a higher degree of freedom to control the pore size. We can say that higher voltage application during the conductometry would accelerate the etching in the tracks. The electrophoretic migration of dissolved products occurring out of each pore might be one of the reasons for this enhanced pore evolution and growth.
Sano, Kenji*; Yamada, Arisa*; Matsui, Akihiro*; Tsuji, Hideyuki*; Hasegawa, Shin; Sawada, Shinichi; Maekawa, Yasunari
Desalination, 324, p.34 - 36, 2013/09
Anchored osmotic pressure inducer was examined. Salt-containing filter paper attached to an osmotic membrane increased the water flux to more than 10% at 1 MPa. The salt-containing filter paper was fabricated via graft polymerization of acrylic acid onto a filter paper followed by alkaline treatment. The filter paper was characterized by thermo gravimetric analysis (TGA), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), scanning electronic microscopy-energy dispersive X-ray spectrometry(SEM-EDS).
Koshikawa, Hiroshi; Yoshimura, Kimio; Sinnananchi, W.; Yamaki, Tetsuya; Asano, Masaharu; Yamamoto, Kazuya*; Yamaguchi, Susumu*; Tanaka, Hirohisa*; Maekawa, Yasunari
Macromolecular Chemistry and Physics, 214(15), p.1756 - 1762, 2013/08
Graft-type anion-conducting polymer electrolyte membranes were prepared by the radiation-induced graft polymerization of chloromethylstyrene into poly(ethylene-co-tetrafluoroethylene) (ETFE) films and subsequent quaternization with trimethylamine to evaluate the counter anion effects on fuel cell properties. The hydroxide form was maintained in -saturated water to prevent the bicarbonate formation. The hydroxide form showed conductivity and water uptake four and two times higher than the chloride and bicarbonate forms. The hydroxide form is thermally and chemically less stable, resulting in the tendency to absorb water and to convert to the bicarbonate form.
Park, J.*; Takayama, Toshio*; Asano, Masaharu; Maekawa, Yasunari; Kudo, Kazuaki*; Takayama, Toshio*
Polymer, 54(17), p.4570 - 4577, 2013/08
Graft-type sulfonated polybenzimidazole was prepared through radiation-induced graft polymerization of styrenes into an alicyclic polybenzimidazole film and subsequent sulfonation. The alicyclic polybenzimidazole, ChPBI, was prepared from -1,4-cyclohexanedicarboxylic acid and 3,3'-diaminobenzidine using typical polycondensation. Anisotropic domains with a size of several tens of micrometers were found in the ChPBI films casted from LiCl-containing ,-dimethylacetamide. Irradiation of the ChPBI membranes with a 220 kGy dose of -rays created radical species with mean lifetimes of two days. The treatment of this membrane with a 50/50 (v/v) mixture of 1-propanol and styrene produced polystyrene graft chains. Sulfonation of the resulting grafted membrane with ClSOHOH occurred selectively on the polystyrene grafts. The sulfonated films showed proton conductivity on the order of 10 to 10 S/cm with an ion exchange capacity between 2.1 and 2.9 mmol/g. SEM-EDX analysis of the membrane indicated the presence of macrophase separated domains up to 1 m in diameter. The proton conductivity of the membrane did not decrease for 600 h at 120C in liquid water.
Sawada, Shinichi; Yamaguchi, Daisuke; Putra, A.; Koizumi, Satoshi*; Maekawa, Yasunari
Polymer Journal, 45(8), p.797 - 801, 2013/08
The nanoscale structures of graft-type polymer electrolyte membranes based on poly(ethylene-co-tetrafluoroethylene) (ETFE) films were investigated using a small-angle neutron scattering (SANS) technique. For comparison, SANS measurements were also performed on two precursor materials, the original ETFE film and polystyrene (PS)-grafted films. The SANS profiles of the grafted films showed shoulder peaks at a d-spacing of approximately 30 nm, which were attributed to the PS grafts introduced into the amorphous phases between the ETFE lamellar crystals. In the ETFE PEMs, the spacing of the polystyrene sulfonic acid (PSSA) grafts and ETFE crystals increased because the graft regions were enlarged by the volume of the attached sulfonic acid groups. Interestingly, the graft / crystal stack spacing in the PEMs did not increase from the dry- to fully-hydrated states. This finding implies restricted water absorption in the PSSA grafts between the ETFE lamellar crystals.
Park, J.; Enomoto, Kazuyuki; Yamashita, Takashi*; Takagi, Yasuyuki*; Todaka, Katsunori*; Maekawa, Yasunari
Journal of Membrane Science, 438, p.1 - 7, 2013/07
Alicyclic polyimides (APIs) were successfully applied to radiation-induced graft polymerization for developing polymer electrolyte membranes for fuel cells. The grafting into fully aromatized polyimide barely proceeded (grafting degrees (GDs) of less than 5%), whereas that of styrene into the API films proceeded with styrene GDs of up to 70%. In combination of electron spin resonance measurements and ultraviolet-visible (UV-VIS) spectroscopy, the radical species was identified as a long-lived intermediate and 10% of the radicals were consumed as grafting initiators. The moderate reaction conditions allowed for selective sulfonation on the polystyrene grafts, and not on the API substrates, to give API-based polymer electrolyte membranes (PEMs) with ion exchange capacities (IEC) of 1.7-2.8 mmol/g. The PEMs exhibited appropriate proton conductivity and low water uptake, together with excellent mechanical properties, compared with conventional PEMs such as Nafion.
Sawada, Shinichi; Yabuuchi, Atsushi*; Maekawa, Masaki; Kawasuso, Atsuo; Maekawa, Yasunari
Radiation Physics and Chemistry, 87, p.46 - 52, 2013/06
The location and size of nanoscale free-volume holes (nanoholes) in graft-type polymer electrolyte membranes (PEMs), which were prepared by radiation-induced graft polymerization (grafting) of styrene into crosslinked-polytetrafluoroethylene (cPTFE) films and subsequent sulfonation, was investigated using positron annihilation lifetime (PAL) spectroscopy. The PAL spectra of the PEMs indicated the existence of two types of ortho-positronium (o-Ps) species, corresponding to nanoholes with volumes of 0.11 and 0.38 nm, respectively. Comparison of the PAL data of the PEMs with that of the precursor original cPTFE and polystyrene-grafted films demonstrated the probability that the smaller holes were located in both the PTFE crystalline phases and the poly(styrene sulfonic acid) graft regions, whereas the larger holes are potentially localized in the PTFE amorphous phases.
Hasegawa, Shin; Takahashi, Shuichi*; Iwase, Hiroki*; Koizumi, Satoshi; Onuma, Masato*; Maekawa, Yasunari
Polymer, 54(12), p.2895 - 2900, 2013/05
Radiation-induced graft polymerization of sulfo-containing styrene derivatives into crystalline poly(ether ether ketone) (PEEK) substrates was carried out to prepare thermally and mechanically stable polymer electrolyte membranes based on an aromatic hydrocarbon polymer, so-called "super-engineering plastics". Graft polymerization of the sulfo-containing styrene, ethyl 4-styrenesulfonate (E4S) into PEEK substrates with degrees of crystallinity (DC) of 11 - 26% gradually progressed, achieving a grafting degree of more than 50% after 72 hours, whereas graft polymerization of the substrates with DC above 26% did not proceed. When morphological change in these films were measured by SAXS, PEEK films with DC larger than 26% showed a new peak at d=14 nm, corresponding to lamella structure. Thus, the suppression of graft polymerization of PEEK films with DC above 26% was due to obstruct of monomer diffusion by the formation of the oriented lamella structure.
Nuryanthi, N.*; Yamaki, Tetsuya; Koshikawa, Hiroshi; Asano, Masaharu; Sawada, Shinichi; Hasegawa, Shin; Maekawa, Yasunari; Katsumura, Yosuke*
Transactions of the Materials Research Society of Japan, 38(1), p.105 - 108, 2013/03
We report here how conditions of the conductometric analysis affected the etching characteristics of 25 m-thick poly(vinylidene fluoride) film irradiated with 450 MeV Xe ions. The etching was performed in a 9 mol dm aqueous potassium hydroxide solution at 80C in a conductometric cell. According to the scanning electron microscope observations, the ion-track membrane obtained with an applied AC voltage of 1.0 V had the surface pores of 16820 nm in diameter. On the other hand, the etching without an applied voltage gave the approximately two-thirds smaller pores. The conductomeric etching would provide a higher degree of freedom for controlling the pore diameter.
Iwase, Hiroki*; Sawada, Shinichi; Yamaki, Tetsuya; Koizumi, Satoshi; Onuma, Masato*; Maekawa, Yasunari
Macromolecules, 45(22), p.9121 - 9127, 2012/11
Fundamental understanding of the structure-property relationship of polymer electrolyte membranes (PEM) is prerequisite for a material design satisfying PEM performance requirement. Small-angle scattering in a wide- range was observed by focusing small-angle neutron scattering (FSANS), small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS). The hierarchical structure of the PEM was characterized as being composed of conducting layers (graft domains) in lamellar stacks with 48-57 nm spacing on the surfaces of 480 nm diameter crystallites and ultra-small structures with a 1.7 nm correlation distance of the sulfonic acid groups in the conducting layers. From the change in the SAXS profiles as a function of grafting degrees, it was revealed that the graft domains around the crystallites were connected with the adjoining domains and thus, the PEMs with a higher degree of grafting had conductivity higher than that of Nafion.