Sawada, Shinichi*; Kimura, Takehiro*; Nishijima, Haruyuki*; Kodaira, Takahide*; Tanaka, Nobuyuki; Kubo, Shinji; Imabayashi, Shinichiro*; Nomura, Mikihiro*; Yamaki, Tetsuya*
International Journal of Hydrogen Energy, 45(27), p.13814 - 13820, 2020/05
An electrochemical membrane Bunsen reaction using a cation exchange membrane (CEM) is a key to achieving an iodine-sulfur (IS) thermochemical water splitting process for mass-production of hydrogen. In this study, we prepared both the radiation-grafted CEM with a high ion exchange capacity (IEC) and the highly-porous Au-electroplated anode, and then used them for the membrane Bunsen reaction to reduce the cell overvoltage. The high-IEC grafted CEM exhibited low resistivity for proton transport, while the porous Au anode had a large effective surface area for anodic SO oxidation reaction. As a result, the cell overvoltage for the membrane Bunsen reaction was significantly reduced to 0.21 V at 200 mA/cm, which was only one-third of that of the previous test using the commercial CEM and non-porous anode. From the analysis of the current-voltage characteristics, employment of the grafted CEM was found to be more effective for the overvoltage reduction compared to the porous Au anode.
Kitamura, Akane; Yamaki, Tetsuya*; Yuri, Yosuke*; Koshikawa, Hiroshi*; Sawada, Shinichi*; Yuyama, Takahiro*; Usui, Aya; Chiba, Atsuya*
Nuclear Instruments and Methods in Physics Research B, 460, p.254 - 258, 2019/12
Poly(vinylidene-fluoride) (PVDF) film is suitable for investigation of the size of etchable ion tracks because we can clearly judge the finish of the track etching and the surrounding bulk area remains due to the high chemical stability. Thereby we can measure the radius of ion tracks of each ion. In this study, we focused on two irradiation conditions for controlling the size of etchable ion tracks of PVDF films. One was irradiation in an oxygen atmosphere and the other was a fullerene (C) cluster beam irradiation. SEM observation showed that the size of pores became larger by irradiation in an oxygen atmosphere. It was found that the oxidation of ion tracks widened the size of etchable ion tracks. The C irradiation caused larger etchable tracks on the PVDF surface. The result could represent the effect of local and simultaneous collisions by the swift aggregated ions.
Kitamura, Akane; Ishikawa, Norito; Kondo, Keietsu; Yamamoto, Shunya*; Yamaki, Tetsuya*
Nuclear Instruments and Methods in Physics Research B, 460, p.175 - 179, 2019/12
Irradiation at grazing incidence formed chains of multiple hillocks on the surface of strontium titanate (SrTiO) and titanium oxide (TiO). They were observed with an atomic force microscope (AFM), however, the AFM measurement gives resolution errors in a nanometer order due to the curvature of the probe tip. To prevent these errors, a field emission scanning electron microscope (FE-SEM) would be a better option for observation. In this study, we performed SEM observations for the chains of the multiple hillocks. Single crystals of SrTiO and TiO were irradiated with 200 MeV Xe in the tandem accelerator at JAEA-Tokai. It was revealed that a lot of isolated hillocks were formed in a line on these surface. The diameter and the interval of those hillocks are discussed in comparison to AFM observation.
Ogawa, Tatsuhiko; Sato, Tatsuhiko; Yamaki, Tetsuya*
Hoshasen Kagaku (Internet), (108), p.11 - 17, 2019/11
Scintillators are generally used to detect various kinds of particles such as electrons, gammas, protons and heavy ions. Scintillators emit photons according to the energy deposited to the crystal. It is also known that light yield is suppressed for particles depositing energy densely owing to quenching. Moreover, it is suggested that quenching is attributed to transfer of energy from excited fluorescent molecules to damaged molecules (Frster mechanism or Dexter mechanism). In this study, energy deposition in a scintillator crystal by radiation was calculated using radiation transport codes to finally obtain excitation and damage of fluorescent molecules. Based on the calculation, spatial configuration of exited and damaged molecules. Then the probability that Frster mechanism takes place in excited molecules were estimated to obtain the number of fluorescent molecules that emit photons. As a result, light yield is proportionally increased with increase in the incident energy in case of electron incidence. On the other hand, light yield is increased non-linearly in case of proton incidence. This trend is in a good agreement with the experimental results.
Inagaki, Yoshiyuki; Sakaba, Nariaki; Tanaka, Nobuyuki; Nomura, Mikihiro*; Sawada, Shinichi*; Yamaki, Tetsuya*
Nippon Kaisui Gakkai-Shi, 73(4), p.194 - 202, 2019/08
The thermochemical IS process is a promising hydrogen production method which can produce hydrogen in a large amount and stably with high efficiency by thermal splitting of water. Research and development on chemical reaction technology with membranes was conducted for the purpose of improving the efficiency of IS process and application of solar heat. The basic technology of ceramic membranes applied to decomposition reactions of hydrogen iodine and sulfuric acid was developed, and it is expected that the conversion rate on decomposition in each reaction can be remarkably improved. The basic technology of a cation exchange membrane applied to Bunsen reaction was developed with radiation-induced grafting technique, it is expected that the amount of iodine can be reduced to about one-fifth compared to the conventional method. These achievements are important technologies for practical use of the IS process.
Sawada, Shinichi*; Yasukawa, Masahiro*; Koshikawa, Hiroshi*; Kitamura, Akane; Higa, Mitsuru*; Yamaki, Tetsuya*
Nippon Kaisui Gakkai-Shi, 73(4), p.208 - 216, 2019/08
For applications to saline water concentration by electrodialysis, we prepared nano-structure-controlled cation and anion exchange membranes (CEMs and AEMs) by a so-called ion-track grafting technique. This new technique involves irradiation of a polymer substrate with an MeV-GeV heavy-ion beam to form the nano-sized cylindrical ion tracks and the graft polymerization only into the ion tracks for the creation of one-dimensional transport pathways. A 25-m-thick poly(ethylene-co-tetrafluoroethylene) film was irradiated with 560 MeV Xe or 310 MeV Kr. The irradiated films were immersed in grafting solutions of ethyl p-styrenesulfonate (EtSS) and chloromethylstyrene (CMS),and then subjected to the hydrolysis of EtSS units and quaternization of CMS units to prepare CEMs and AEMs, respectively. These CEMs and AEMs showed lower resistance than the commercially-available membranes even at the very low water uptake. This would be due to the signifcantly-effcient transport of ions through the unique one-dimensional highly-connected transport pathways. In the saline water concentration experiment, a pair of our CEM and a commercial AEM or vice versa led to a higher salt concentration in the concentration chamber than did a pair of the commercial membranes. This result demonstrated great applicability of our ion-track-grafted CEMs and AEMs for saline water concentration.
Myagmarjav, O.; Iwatsuki, Jin; Tanaka, Nobuyuki; Noguchi, Hiroki; Kamiji, Yu; Ioka, Ikuo; Kubo, Shinji; Nomura, Mikihiro*; Yamaki, Tetsuya*; Sawada, Shinichi*; et al.
International Journal of Hydrogen Energy, 44(35), p.19141 - 19152, 2019/07
Kitamura, Akane; Ishikawa, Norito; Kondo, Keietsu; Fujimura, Yuki; Yamamoto, Shunya*; Yamaki, Tetsuya*
Transactions of the Materials Research Society of Japan, 44(3), p.85 - 88, 2019/06
Swift heavy ions can create nanosized hillocks on the surfaces of various ceramics. When these materials are irradiated with swift heavy ions at normal incidence, each ion impact results in the formation of a single hillock on the surfaces. In contrast, irradiation at grazing incidence forms chains of multiple hillocks on the surface, for example, for strontium titanate (SrTiO). So far, chains of multiple hillocks have been investigated using atomic force microscopy (AFM). It should be noted that AFM measurements involve systematic errors of several nanometers due to the finite size of the probe tip. Consequently, it is possible that the image of one hillock may merge with that of a neighboring hillock even if the two hillocks are well separated. In contrast to AFM, field-emission scanning electron microscopy (FE-SEM) is a useful technique for obtaining higher-resolution images. In this study, we observed multiple nanohillocks on the surfaces of SrTiO using FE-SEM. Crystals of SrTiO(100) and 0.05 wt% Nb-doped SrTiO(100) were irradiated with 350 MeV Xe ions, respectively, at grazing incidence, where the angle between the sample surface and the beam was less than 2. On the SrTiO surface, a chain of periodic nanohillocks is created along the ion path. In contrast, black lines accompanied by hillocks are observed on the Nb-doped SrTiO surface.
Kakitani, Kenta*; Kimata, Tetsuya*; Yamaki, Tetsuya*; Yamamoto, Shunya*; Matsumura, Daiju; Taguchi, Tomitsugu*; Terai, Takayuki*
Radiation Physics and Chemistry, 153, p.152 - 155, 2018/12
Yamaki, Tetsuya*; Nuryanthi, N.*; Kitamura, Akane; Koshikawa, Hiroshi*; Sawada, Shinichi*; Voss, K.-O.*; Severin, D.*; Tautmann, C.*
Nuclear Instruments and Methods in Physics Research B, 435, p.162 - 168, 2018/11
We used individual single-ion tracks in fluoropolymers with diameters of tens to hundreds of nanometers; chemical etching and ion-track grafting enabled us to develop ion-track and proton-conductive membranes, respectively. In the ion-track membranes of PVDF, strongly-LET-dependent etching was found, so the pore shape as well as the size was exclusively controlled by the track structures. We performed the ion-track grafting of styrene into ETFE to develop nanostructure-controlled proton exchange membranes (PEMs) for applications in PEM fuel cells. Our ion beam technology to develop fluoropolymer-based nanostructures has the potential to apply in the field of filtration processes and fuel cell devices. This would make it possible to provide new microfiltration technology for water treatment, sterilization, petroleum refining and dairy processing.
Nomura, Mikihiro*; Kodaira, Takahide*; Ikeda, Ayumi*; Naka, Yasuhito*; Nishijima, Haruyuki*; Imabayashi, Shinichiro*; Sawada, Shinichi*; Yamaki, Tetsuya*; Tanaka, Nobuyuki; Kubo, Shinji
Journal of Chemical Engineering of Japan, 51(9), p.726 - 731, 2018/09
Thermochemical hydrogen production by the iodine-sulfur process decomposes water into hydrogen and oxygen by combining the chemical reactions of iodine and sulfur. Two types of acids are produced through the Bunsen reaction. To improve the performance of this reaction, ion-exchange membranes for the membrane Bunsen reaction should be developed. In the present study, a cation-exchange membrane was prepared by using a radiation-graft polymerization method. It was found that a divinylbenzene crosslinking procedure was very effective in reducing water permeation through the membrane, and the membrane Bunsen reaction was successfully carried out by using the developed crosslinked membrane. Therefore, the developed crosslinked membrane is a potential candidate for cation-exchange membranes for the membrane Bunsen reaction.
Ogawa, Tatsuhiko; Yamaki, Tetsuya*; Sato, Tatsuhiko
PLOS ONE (Internet), 13(8), p.e0202011_1 - e0202011_19, 2018/08
Scintillators are generally used to detect various kinds of particles such as electrons, gammas, protons and heavy ions. Scintillators emit photons according to the energy deposited to the crystal. It is also known that light yield is suppressed for particles depositing energy densely owing to quenching. Moreover, it is suggested that quenching is attributed to transfer of energy from excited fluorescent molecules to damaged molecules (Frster mechanism). In this study, energy deposition in a scintillator crystal by radiation was calculated using radiation transport codes to finally obtain excitation and damage of fluorescent molecules. Based on the calculation, spatial configuration of exited and damaged molecules. Then the probability that Frster mechanism takes place in excited molecules were estimated to obtain the number of fluorescent molecules that emit photons. As a result, light yield is proportionally increased with increase in the incident energy in case of electron incidence. On the other hand, light yield is increased non-linearly in case of proton incidence. This trend is in a good agreement with the experimental results.
Yamaki, Tetsuya*; Kitamura, Akane; Sawada, Shinichi*; Koshikawa, Hiroshi*
Nippon Kaisui Gakkai-Shi, 72(2), p.62 - 74, 2018/04
This review paper is devoted to two topics, i.e., fluoropolymer-based porous and ion-exchange membranes, both of which include the creation of nanostructure-controlled functional membranes with high-energy ion beams. Latent tracks of the MeV-GeV heavy ions in a polymer foil can sometimes be chemically etched out to form a membrane with micro- and nano-sized through-pores, the so-called ion-track membrane. Our focus is on ion-track membranes of poly (vinylidene fluoride) (PVDF) and cation- and anion-exchange membranes (CEMs and AEMs, respectively).
Kitamura, Akane; Yamaki, Tetsuya*; Chiba, Atsuya*; Usui, Aya
QST-M-8; QST Takasaki Annual Report 2016, P. 37, 2018/03
We investigated the track-etched surface of PVDF films irradiated with C cluster ions, comparing the data with C monoatomic ions. PVDF films were irradiated with 6 MeV C cluster ions. The energy of the each carbon ion is 100 keV/atom; thus, for comparison, the PVDF films were also irradiated with 100 keV C ions. SEM and AFM observation showed that the surface irradiated with C cluster ions apparently possessed flat-bottomed pores with an average diameter and depth of approximately 400 and 250 nm, respectively. On the other hand, track-etched pores were also formed on the surface irradiated with C ions, but their morphology was irregular or obscure. In the irradiation with the C cluster ions, the surface diameter of track-etched pores increased with increasing the etching time. The tracks of the 100 keV C ions seemed to be hardly developed by the etching when the time. In conclusion, the C cluster ions irradiation caused a large size of etchable tracks on the PVDF surface. The result could represent the effect of local and simultaneous collision by the aggregated ions.
Yamaki, Tetsuya*; Goto, Mitsuaki*; Sawada, Shinichi*; Koshikawa, Hiroshi*; Kitamura, Akane; Higa, Mitsuru*
QST-M-8; QST Takasaki Annual Report 2016, P. 35, 2018/03
We prepared ion exchange membranes by a heavy-ion-track grafting method, and then used them for seawater concentration process. Both the water uptake and resistance were lower for our ion-track grafted membranes than for the conventional -ray-grafted membranes. The results would be because local and high-density energy deposition due to the ion beam enabled us to control the membrane structure in a nanometer scale. We demonstrate our membranes are suitable for this application.
Ogawa, Tatsuhiko; Yamaki, Tetsuya*; Sato, Tatsuhiko
QST-M-2; QST Takasaki Annual Report 2015, P. 46, 2017/03
Modification of materials by irradiation, which is substantially important for radiation safety in facilities and industrial applications, is studied from various aspects. Material modification is induced by local energy deposition by incident radiation followed by the changes of chemical bonds in the spatial scale of nm to m. So far, absorbed dose was regarded as the best index of irradiation effects, however, it is also known that irradiation effects varies depending on the radiation species even under the same absorbed dose or LET. Radiation transport simulation code PHITS can calculate simulate energy deposition in nm to m scale to obtain LET and specific energy deposition (SED). By using SED calculation function, an attempt to reproduce radiation species dependence of material property change based on the theoretical prediction of chemical reactions induced by energy deposition in different irradiation conditions. Estimate on the decrease in Elongation at Break (EB) of poly-ether sulfone in three different irradiation conditions, 10 MeV protons, 50 MeV He and C showed that reduction of EB by carbon ions is twice as small as that by proton and that by helium for the same absorbed dose, which is in an agreement with experiment. Moreover, assuming that scission of polymer takes place at random and 100 eV energy deposition in the region result in loss of mechanical strength, saturating trend of EB reduction.
Eichler, R.*; Asai, Masato; Brand, H.*; Chiera, N. M.*; Di Nitto, A.*; Dressler, R.*; Dllmann, Ch. E.*; Even, J.*; Fangli, F.*; Goetz, M.*; et al.
EPJ Web of Conferences (Internet), 131, p.07005_1 - 07005_7, 2016/12
In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the productions and investigations of fragile single molecular species of superheavy elements. The latest highlight is the formation of very volatile hexacarbonyl compound of element 106, Sg(CO). Following this success, second-generation experiments were performed to measure the first bond dissociation energy between the central metal atom and the surrounding ligand. The method using a tubular decomposition reactor was developed and successfully applied to short-lived Mo(CO), W(CO), and Sg(CO).
Usoltsev, I.*; Eichler, R.*; Wang, Y.*; Even, J.*; Yakushev, A.*; Haba, Hiromitsu*; Asai, Masato; Brand, H.*; Di Nitto, A.*; Dllmann, Ch. E.*; et al.
Radiochimica Acta, 104(3), p.141 - 151, 2016/03
Conditions of the production and decomposition of hexacarbonyl complexes of short-lived Mo and W isotopes were investigated to study thermal stability of the heaviest group 6 hexacarbonyl complex Sg(CO). A tubular flow reactor was tested to decompose the hexacarbonyl complexes and to extract the first bond dissociation energies. A silver was found to be the most appropriate reaction surface to study the decomposition of the group 6 hexacarbonyl. It was found that the surface temperature at which the decomposition occurred was correlated to the first bond dissociation energy of Mo(CO) and W(CO), indicating that the first bond dissociation energy of Sg(CO) could be determined with this technique.
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.
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.