Pressure-driven solid-state radical polymerization toward carbon nanothread

Che, G.*; Tang, X.*; Liu, J.*; Lang, P.*; Fei, Y.*; Yang, X.*; Wang, Y.*; Gao, D.*; Wang, X.*; Ju, J.*; et al.

Nano Letters, 25(39), p.14467 - 14472, 2025/09

https://doi.org/10.1021/acs.nanolett.5c03977

機械化学的ラジカル重合は、溶媒消費量の削減と不溶性モノマーへの適応性により、ポリマー合成において独自の利点を有する。しかしながら、反応中に生成ポリマーが制御不能に分解するという課題があり、精密な制御性を備えた新たな合成戦略の開発が求められている。本研究では、最大30GPaの高静圧を適用することで、1,3,5-トリフルオロベンゼンが共役結合を切断するラジカル重合を起こし、高選択性でカーボンナノスレッド(ポリマーI多形体)を形成することを発見した。閾値圧力における結晶構造と結合経路の計算エネルギー障壁に基づき、ベンゼン環が1-2ラジカル重合経路で反応すると結論付けた。本研究は、極めて安定な芳香族化合物に対しても固相ラジカル重合を開始する堅牢な手法として高圧が有効であることを示し、高選択性を持つ炭素系高分子材料の合成に向けた新たな知見を提供する。

Ordered graphane nanoribbons synthesized via high-pressure diels-alder polymerization of 2,2'-bipyrazine

Li, F.*; Tang, X.*; Fei, Y.*; Zhang, J.*; Liu, J.*; Lang, P.*; Che, G.*; Zhao, Z.*; Zheng, Y.*; Fang, Y.*; et al.

Journal of the American Chemical Society, 147(17), p.14054 - 14059, 2025/04

https://doi.org/10.1021/jacs.5c03116

2,2'-ビピラジン(BPZ)の圧力誘起重合により結晶性グラファンナノリボン(GANR)を合成した。中性子回折データのリートベルト精密化,核磁気共鳴スペクトル,赤外スペクトル,理論計算を行った結果、BPZは 積層した芳香環の間でディールス・アルダー重合し、並外れた長距離秩序を持つ伸びたボート型GANR構造を形成することがわかった。未反応の-C=N-基がボートの両端を橋渡ししており、さらなる機能化の余地がある。このGANRのバンドギャップは2.25eVであり、光電応答は良好である(I/I =18.8)。われわれの研究は、高圧トポケミカル重合法が、特定の構造と望んだ特性を持つグラファンの精密な合成に有望な方法であることを強調している。

Pressure-induced polymerization of 1,4-difluorobenzene towards fluorinated diamond nanothreads

Che, G.*; Fei, Y.*; Tang, X.*; Zhao, Z.*; 服部 高典; 阿部 淳*; Wang, X.*; Ju, J.*; Dong, X.*; Wang, Y.*; et al.

Physical Chemistry Chemical Physics, 27(2), p.1112 - 1118, 2025/01

https://doi.org/10.1039/D4CP03751K

芳香族分子の圧力誘起重合(PIP)は、様々な炭素系材料を合成するための効果的な方法として浮上してきた。目的とする構造や機能を得るためには、適切な官能基化された分子前駆体の選択が極めて重要である。本研究では、1,4-ジフルオロベンゼン(1,4-DFB)をPIPの構成要素として選択した。1,4-DFBをその場高圧で調べた結果、約12.0GPaで相転移が起こり、18.7GPaで不可逆的な化学反応が起こることがわかった。生成物の構造解析と反応のカイネティクスから、直線的な成長を伴う擬六方晶積層フッ素ダイヤモンドナノスレッドの形成が明らかになった。高圧下のベンゼンの結晶構造と比較して、1,4-DFBは[001]軸に沿って高い圧縮を示す。この異方的な圧縮は、[01]軸に沿ったより強いH相互作用と、[100]軸と[010]軸に沿った潜在的な圧縮阻害HF相互作用に起因し、[01]軸に沿った可能な反応経路を促進する。この研究は、分子スタッキングを調節し、反応経路に影響を与える官能基化の重要な役割を強調している。

Si-addition contributes to overcoming the strength-ductility trade-off in high-entropy alloys

Wei, D.*; Gong, W.; 都留 智仁; Lobzenko, I.; Li, X.*; Harjo, S.; 川崎 卓郎; Do, H.-S.*; Bae, J. W.*; Wagner, C.*; et al.

International Journal of Plasticity, 159, p.103443_1 - 103443_18, 2022/12

https://doi.org/10.1016/j.ijplas.2022.103443

Face-centered cubic single-phase high-entropy alloys (HEAs) containing multi-principal transition metals have attracted significant attention, exhibiting an unprecedented combination of strength and ductility owing to their low stacking fault energy (SFE) and large misfit parameter that creates severe local lattice distortion. Increasing both strength and ductility further is challenging. In the present study, we demonstrate via meticulous experiments that the CoCrFeNi HEA with the addition of the substitutional metalloid Si can retain a single-phase FCC structure while its yield strength (up to 65%), ultimate strength (up to 34%), and ductility (up to 15%) are simultaneously increased, owing to a synthetical effect of the enhanced solid solution strengthening and a reduced SFE. The dislocation behaviors and plastic deformation mechanisms were tuned by the addition of Si, which improves the strain hardening and tensile ductility. The present study provides new strategies for enhancing HEA performance by targeted metalloid additions.

Phase transition and chemical reactivity of 1H-tetrazole under high pressure up to 100 GPa

Gao, D.*; Tang, X.*; Wang, X.*; Yang, X.*; Zhang, P.*; Che, G.*; Han, J.*; 服部 高典; Wang, Y.*; Dong, X.*; et al.

Physical Chemistry Chemical Physics, 23(35), p.19503 - 19510, 2021/09

https://doi.org/10.1039/D1CP02913D

窒素に富む分子の圧力有機相転移や重合は、環境にやさしい高エネルギー密度材料の開発にとって非常に重要であるため、広く注目されている。本論文では、その場ラマン,IR,X線回折,中性子回折、および理論計算をもちい、100GPaまでの1H-テトラゾールの相転移挙動と化学反応の研究を紹介する。2.6GPa以上での相転移が確認され、その高圧構造は、以前に報告されたユニットセル内に2つの分子をもつものではなく、1つの分子をものであることが分かった。1H-テトラゾールは、おそらく窒素-窒素結合ではなく炭素-窒素結合により、100GPa以下で可逆的に重合する。私たちの研究は、1H-テトラゾールの高圧相の構造モデルを更新し、もっともらしい分子間結合の経路を初めて提示した。これにより、窒素に富む化合物の相転移と化学反応の理解が進み、新しい高エネルギー密度材料の設計に役立つと考えられる。

Simultaneous determination of neutron-induced fission and radiative capture cross sections from decay probabilities obtained with a surrogate reaction

Prez Snchez, R.*; Jurado, B.*; Mot, V.*; Roig, O.*; Dupuis, M.*; Bouland, O.*; Denis-Petit, D.*; Marini, P.*; Mathieu, L.*; Tsekhanovich, I.*; et al.

Physical Review Letters, 125(12), p.122502_1 - 122502_5, 2020/09

https://doi.org/10.1103/PhysRevLett.125.122502

Reliable neutron-induced-reaction cross sections of unstable nuclei are essential for nuclear astrophysics and applications but their direct measurement is often impossible. The surrogate-reaction method is one of the most promising alternatives to access these cross sections. In this work, we successfully applied the surrogate-reaction method to infer for the first time both the neutron-induced fission and radiative capture cross sections of Pu in a consistent manner from a single measurement. This was achieved by combining simultaneously measured fission and -emission probabilities for the Pu(He, He') surrogate reaction with a calculation of the angular-momentum and parity distributions populated in this reaction. While other experiments measure the probabilities for some selected -ray transitions, we measure the -emission probability. This enlarges the applicability of the surrogate-reaction method.

Search for decay of Te with a novel recoil-decay scintillation detector

Xiao, Y.*; Go, S.*; Grzywacz, R.*; Orlandi, R.; Andreyev, A. N.; 浅井 雅人; Bentley, M. A.*; de Angelis, G.*; Gross, C. J.*; Hausladen, P.*; et al.

Physical Review C, 100(3), p.034315_1 - 034315_8, 2019/09

https://doi.org/10.1103/PhysRevC.100.034315

A search for super-allowed decay of N=Z nuclei Te and Xe was carried out using a novel recoil-decay scintillator detector at the tandem accelerator facility at Japan Atomic Energy Agency. Inorganic crystal scintillation material of YAP:Ce (Yttrium Aluminium Perovskite) coupled to position-sensitive photo-multiplier tube (PSPMT) was implemented for the first time in a radioactive decay experiment. Residues from the fusion-evaporation reaction Ni+Fe Xe were separated by the JAEA Recoil Mass Separator (RMS) and implanted into the YAP:Ce crystal. decays of neutron-deficient tellurium isotopes were identified and proton-emission of I was observed. No conclusive evidence was found for the decay chain XeTe Sn within 3 days experiment. The cross section limit of 130 pb was obtained for production of two events of Xe, about an order of magnitude below the expectation based on earlier cross section measurements and HIVAP calculations.

Fusion reaction Ca+Bk leading to formation of the element Ts (Z=117)

Khuyagbaatar, J.*; Yakushev, A.*; Dllmann, Ch. E.*; Ackermann, D.*; Andersson, L.-L.*; 浅井 雅人; Block, M.*; Boll, R. A.*; Brand, H.*; Cox, D. M.*; et al.

Physical Review C, 99(5), p.054306_1 - 054306_16, 2019/05

AA2019-0039.pdf:5.03MB

https://doi.org/10.1103/PhysRevC.99.054306

Ca+B融合反応を用いて117番元素(Ts)合成実験を行い、117番元素に起因すると思われる4つの崩壊連鎖を観測した。うち2つは長い崩壊連鎖で、Tsの崩壊に起因するものと同定された。他の2つは短い崩壊連鎖で、Tsの崩壊に起因すると考えると矛盾しない。今回の結果と過去の文献値を比較したところ、今回の我々の結果は過去の文献値をほぼ再現し、117番元素合成の事実を強く再確認する結果となった。

Overview of the IFMIF/EVEDA project

Knaster, J.*; Garin, P.*; 松本 宏*; 奥村 義和*; 杉本 昌義*; Arbeiter, F.*; Cara, P.*; Chel, S.*; Facco, A.*; Favuzza, P.*; et al.

Nuclear Fusion, 57(10), p.102016_1 - 102016_25, 2017/06

https://doi.org/10.1088/1741-4326/aa6a6a

The International Fusion Materials Irradiation Facility (IFMIF) is presently in its engineering validation and engineering design activities phase. The engineering design phase was successfully accomplished. The engineering validation activity has focused on validating the Accelerator Facility, the Target Facility and the Test Facility by constructing prototypes. The EVEDA Lithium Test Loop (ELTL) at JAEA successfully demonstrated the long-term stability of a Li flow under the IFMIF's nominal operational conditions keeping the specified free-surface fluctuations below 1 mm in a continuous manner for 25 days. A full-scale prototype of the high flux test module was successfully tested in the Helium Loop Karlsruhe (HELOKA), where it was demonstrated that the irradiation temperature can be set individually and kept uniform. LIPAc Accelerator, designed and constructed in European labs under the coordination of F4E and JAEA, presently under installation and commissioning in the Rokkasho Fusion Institute, aims at validating the concept of IFMIF accelerators with a D beam of 125 mA continuous wave and 9 MeV. The commissioning phases of the H/D beams at 100 keV were progressing and should be concluded in 2017; in turn, the commissioning of the 5 MeV beam was due to start during 2017. The D beam through the superconducting cavities is expected to be achieved with the superconducting cryomodule being assembled in Rokkasho.

Identification of the crossing point at = 21 between normal and intruder configurations

Lic, R.*; Rotaru, F.*; Borge, M. J. G.*; Grvy, S.*; Negoita, F.*; Poves, A.*; Sorlin, O.*; Andreyev, A. N.; Borcea, R.*; Costache, C.*; et al.

Physical Review C, 95(2), p.021301_1 - 021301_6, 2017/02

https://doi.org/10.1103/PhysRevC.95.021301

The decay of Mg was used to study the Al nucleus through spectroscopy at the Isotope Separator On-Line facility of CERN. Previous studies identified two -decaying states in Al having spin-parity assignments =4 dominated by the normal configuration (d5/2) (f7/2) and = 1 by the intruder configuration (d5/2) (d3/2)(f7/2). Their unknown ordering and relative energy have been the subject of debate for the placement of Al inside or outside the = 20 "island of inversion". We report here that the 1 intruder lies only 46.6 keV above the 4 ground state. In addition, a new half-life of =44.9(4)ms, that is twice as long as thepreviously measured 20(10) ms, has been determined for Mg. Large-scale shell-model calculations with the recently developed SDPF-U-MIX interaction are compared with the new data and used to interpret the mechanisms at play at the very border of the = 20 island of inversion.