CONCLUSION
常磁性物質内における分子運動のマジック角回転 2 H-NMRスペクトル による研究
Motohiro Mizuno
a,, You Suzuki
a, Masataka Tansho
b, and Tadashi Shimizu
b 水野元博a,
鈴木陽a、丹所正孝b、清水禎ba
Department of Chemistry, Graduate School of Natural Science and Technology, Kanazawa University,
b
National Institute for Materials Science,
a金沢大学、
b物質・材料研究機構A magic-angle spinning (MAS)
2H NMR experiment was applied to study the molecular motion in paramagnetic compounds. The temperature dependences of
2H MAS NMR spectra were measured for paramagnetic [M(H
2O)
6]-[SiF
6] (M = Ni
2+,Mn
2+, Co
2+) and diamagnetic [Zn(H
2O)
6][SiF
6]. The paramagnetic compounds exhibited an asymmetric line shape in
2H MAS NMR spectra because of the electron-nuclear dipolar coupling.
The drastic changes in the shape of spinning sideband patterns and in the line width of spinning sidebands due to the 180flip of water molecules and the reorientation of [M(H
2O)
6]
2+about its C
3axis were observed. In the paramagnetic compounds, paramagnetic spin-spin relaxation and anisotropic g-factor result in additional linebroadening of each of the spinning sidebands. The spectral simulation of MAS
2H NMR, including the effects of paramagnetic shift and anisotropic spin-spin relaxation due to electron-nuclear dipolar coupling and anisotropic g-factor, was performed for several molecular motions. Information about molecular motions in the dynamic range of 10
2s
-1<k< 10
8s
-1can be obtained for the paramagnetic compounds from the analysis of
2H MAS NMR spectra when these paramagnetic effects are taken into account.
常磁性物質における分子運動を調べるため、常磁性物質[M(H2O)6][SiF6] (M=Ni2+, Mn2+, Co2+)お よび反磁性物質[Zn(H2O)6][SiF6]についてマジック角回転2H-NMR測定を行った。常磁性物質で は、通常、電子-核スピン間の双極子結合により共鳴線が非対称となるが、水分子の180度反転運 動と[M(H2O)6]の回転が生じると2Hのスピニングサイドバンド共鳴線の形状に劇的な変化が観測 される。これらに加え、常磁性スピン-スピン緩和と非等方的なｇ因子を考慮に入れて 2 H-MAS-スペクトルを解析することで、約100Hzから100MHｚまでの分子運動についての詳細な情報を 得ることが可能である。
Results and Conclusion
In thist work, the effects of molecular motion such as a 180° flip of water molecules and reorientation of [M(H
2O)
6]
2+about its C
3axis on the
2H MAS NMR spectra were investigated for paramagnetic [M(H
2O)
6][SiF
6] (M) Ni
2+, Mn
2+, Co
2+) and diamagnetic [Zn(H
2O)
6][SiF
6]. The dynamics of molecules and electron spin in these compounds have been investigated by the
2H NMR spectrum of a single crystal, the
2H NMR broadline spectrum, and T
1of the powder samples.
In the
2H MAS NMR spectra of paramagnetic compounds, the dipolar interaction between the deuteron and the paramagnetic ions causes an asymmetric spinning sideband pattern. Previously, the line shape of
2H MAS NMR spectra in paramagnetic compounds had been investigated only in slow and fast limit motion regimes. We
discuss the effects of intermediate time scale
molecular motions on
2H MAS NMR spectra in
paramagnetic compounds. For the
2H MAS NMR
spectra of paramagnetic compounds, the
anisotropy of the g-factor of paramagnetic ions
and the fast spin-spin relaxation due to the dipolar
interaction between the deuteron and the
paramagnetic ions, as well as molecular motion,
affect largely the line width of the spinning
sideband. The
2H MAS NMR spectral simulation,
including the effects of paramagnetic shift,
anisotropic g-factor, and anisotropic spinspin
relaxation due to the dipolar interaction between
the deuteron and the paramagnetic ions in the
presence of the molecular motion, was performed
using not only the nearest paramagnetic ion but
also the distant ones. When the broadening of the
linewidths are caused by the fast paramagnetic
transverse relaxation, the imaginary part of the spectral density gives rise to the shift in the resonance frequency, often referred to as the dynamic frequency shift (DFS). The effects of DFS to the
2H MAS NMR spectrum were also investigated. A point dipole model was used for the calculation of the dipolar interaction between the deuteron and the paramagnetic ions. The simulation spectrum was obtained by stepwise integration for the equation of the time evolution of magnetization. Application of the proposed simulation method to the analysis of molecular dynamics in paramagnetic samples is discussed by comparing the results of
2H NMR MAS spectra and broadline spectra for paramagnetic [M(H
2O)
6][SiF
6] (M = Ni
2+, Mn
2+, Co
2+) and diamagnetic [Zn(H
2O)
6][SiF
6].
Figure 1. Six-site jump of deuterons caused by the 180flip of water molecules and the three-site jump of [M(H2O)6]2+ about the C3 axis.
Figure 2. Temperature dependence of 2H MAS NMR spectra for diamagnetic [Zn(H2O)6][SiF6]. Observed (a) and simulated (b) spectra.
Figure 3. Temperature dependence of 2H MAS NMR spectra for paramagnetic [Ni(H2O)6][SiF6] in the temperature range of 296-358 K. Observed (a) and simulated (b) spectra.
Figure 4. Temperature dependence of 2H MAS NMR spectra for paramagnetic [Ni(H2O)6][SiF6] in the temperature range of 438-493 K. Observed (a) and simulated (b) spectra.
共同研究型支援 強2008-6
930MHz固体NMRによるオレフィン重合用触媒の構造解析 Ti-NMR in Zigler-Natta Catalyst by High-Field Solid-State NMR
齋藤雅由a、藤田孝a、清水禎b 、出口健三b
Masayoshi Saito
a, Takashi Fujita
a, Tadashi Shimizu
b, Kenzo Deguchi
ba東邦チタニウム、b物質・材料研究機構
a
Toho Titanium Co. Ltd.,
bNational Research Institute for Materials Science
チーグラー・ナッタ触媒の研究は多くの機関より報告されている。とりわけ、触媒活性中心金属 であるTi元素の存在については、各方面より報告されている。しかし、Ti元素の状態を直接測定 できる技術が少ないため、触媒構造の本格的な理解には至っていない。今回我々は、NIMSの強磁 場固体NMRを用いて触媒中のTi元素の測定に成功したので報告する。また、同時にエチレン重合 を実施し、Ti元素の状態と重合活性の相関を調べたので併せて報告する。
We measure
47,49Ti solid-state NMR of Ziegler-Natta catalysts,which are applied to synthesize polyethylene.
We synthesize the catalysts with milling MgCl
2and TiCl
4for 0, 2, 5, and 20 hours, and find interesting behaviour in their
47,49Ti NMR spectra. To explain the behaviour, we propose a model, that
47,49Ti nuclei chemically exchange between liquidlike
47,49Ti and solid-like
47,49Ti in the catalysts.
背景と目的
本研究は、ポリエチレン(PE)およびポリプロ ピレン(PP)といった汎用樹脂の生産に使用す るチーグラー・ナッタ（ZN）触媒の構造につ いて、NIMSの強磁場固体NMRを用いて研究 したものである。
現在PEおよびPPの研究開発の主要課題の ひとつは、高剛性や高強度といった高性能 PE,PPの開発である。しかし、この開発を促進 するためには精密な触媒設計とそれに基づく 触媒開発が必要である。また、ZN触媒発見か ら６０年近くなり、種々の改良をなされている が、この触媒の主成分であるMgCl2、TiCl4お よび電子供与体の相互作用については充分に 判っていない。TiCl4中のTi元素がPE,PP重合 の中心金属（活性点）と言われており、Ti元素、
MgCl2および電子供与体との相互作用が正確 に判れば、高機能PE,PP用触媒の設計に活用が できることを期待される。
ZN触媒の原子レベルでの構造を決定できる
手法として、固体NMRがある。しかし従来の 固体NMRでの報告は、測定が比較的容易な元 素である電子供与体中の炭素元素の変化で議 論をしてきた。触媒中心金属であるTi元素の状 態についての測定には、従来は不可能であった がNIMSの強磁場固体NMRによって観測が初 めて可能になってきた。実験の内容と結果
MgCl2とTiCl4から成る触媒を合成し、この 装置を用いてTi元素核のNMR測定を試みた。
結果を図１に示す。
測定の結果、固体触媒中のTi元素測定が行え ることを「世界で初めて確認することに成功」
した。なお、このNMR信号は、向かって左側 が質量数49Ti、右側が47Ti元素である。
Fig.1: 27,29Ti NMR Spectra in a ZN-catalyst.
この結果をふまえ、以下の試験を試みた。試験 使用触媒は、MgCl2とTiCl4を振動ミルにて共 粉砕し、粉砕時間を0～20時間に変化させたも のである。この触媒のTi元素の状態を強磁場固 体NMRを用いて測定した。同時にPE重合を実 施し、Ti元素状態と重合活性の相関を調べた (図２、３)。
Fig.2: 47,49Ti NMR spectra of TiCl4 (neat liquid) (top) and ZN catalysts at milling time of 0, 2, 5 and 20 hours.
Fig.3: Correlation between milling time and yield of polyethylene for 1g of ZN catalysts.
信号が右側（高磁場側）にシフトした（図２）。
一方、PE重合に関しては、共粉砕時間を長く することで活性が向上していくことを確認（図 ３）した。このことから、共粉砕時間を変化す ることで、チタンNMRスペクトルと活性向上の 相関関係があることが判明した。
考察と今後の課題
このように、強磁場NMRを用いることで、
触媒の原子レベルでの構造解析が容易になり つつあり、今後の高機能PE,PP用触媒の設計の 進捗を計ることが期待される。
発表リスト（誌上・口頭）
誌上発表
[ 1] Quantum interfrence in the quasi-one-dimensional organic conductor (Per)2Au(mnt)2 D.Graf , J.S.Brooks , E.S.Choi , M.Almeida , R.T.Henriques , J.C.Dias , S.Uji
PHYSICAL REVIEW B , vol.75 , p245101-1～p. 245101-5 , 2007
[ 2] Antiferromagnetic ordering of the incommensurate organic superconductor (MDT-TS) (AuI2) (0.441) with a high spin-flop field T.Kawamoto , Y.Bando , T. Mori, T. Konoike , K.Takimiya , T.Otsubo , S.Uji , T.terashima , T.Yamaguchi
PHYSICAL REVIEW B , Vol.77/No.22/p.224506-1～5 , 2008
[ 3] De haas-van Alpen effect in the mixed state of LuNi2B2C: Anisotropy and field dependence of the damping due to superconductivity
T. Isshiki , Kimura , T.Terashima , S.Uji , K. Yamauchi , H. Harima , D. Jaiswal-Nagar , A. K. Grover PHYSICAL REVIEW B , vol. 78/ No. 13/ p.p. 134528-1～134528-12 , 2008
[ 4] Fermi Surface in LaRHSi and CeRhSi3
T.Terashima , M.Kimata , S.Uji , T.Sugawara , N.Kimura , H.Aoki , H.Harima PHYSICAL REVIEW B, Vol.78/No.20/p.205107-1～p.205107-10, 2008
[ 5] Effect of pressure on the steplike magnetostriction of single crystalline bilayered manganite (La0.4Pr0.6)1.2Sr1.8Mn2O7 Y. Yamato, M. Matsukawa, T. Kumagai, R. Suryanarayanan, S. Nimori, M. Apostu, A. Revcolevschi, K. Koyama, N. Kobayashi
Phys. Rev. B78,(2008)132411-1-4.
[ 6] Fermi Surface Properties of CeRu2(SiⅠ-Gex)3 in Magnetic Fields above the MetamagneticTransitions M.Sugi Y.matsumoto N.Kimura T.komatubara H.Aoki T.TERASHIMA ShinyaUj
PHYSICAL REVIEW LETTERS, Vol.101 , No.5 , 056401-1～056401-4, 2008.
[ 7] Possible Phase Transition Deep Inside the Hidden Order Phase of Ultraclean URu2Si2
H. Shishido, K. Hashimoto, T. Shibauchi, T. Sasaki, H. Oizumi, N. Kobayashi, T. Takamasu, K. Takehana, Y. Imanaka, T. D. Matsuda, Y. Haga, Y. Onuki, and Y. Matsuda
To be published in Physical Review Letters
[ 8] Se77 NMR evidence of the Jaccarino-Peter mechanism in the field induced superconductor, -(BET)2FeCl4 K. Hiraki H. Mayaffre M. Morvatic C. Berthier S.Uji T.Yamaguchi A.Kobayashi H.Tanaka T.Yakahashi JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN , Vol.76/No.12/p.124708-1～7 , 2006
[ 9] NMR Study of YbAl3C3 in High Magnetic field
Satoru Tomisawa, Takeshi Mito, Shinji Wada, Kenjiro Hashi, Tadashi Shimizu, Atsushi Goto, Shinobu Ohki, Yoshiaki Kato and Masashi Kosaka,
Journal of the Physical Society of Japan 77 (2008) Supplement A, 291-293
[ 10] Continuous Evolution of Fermi Surface Properties abobe Metamagnetic Transitions in CexLal-xRu2Si2 Y.Matsumoto M.Sugi N.Kimura T.Komatsubara H.Aoki I.SatohT.Terashima S.Uji
JOURNAL OF PHYSICAL SOCIETY OF JAPAN , Vol.77 Number5,page053703-1～053703-4, 2008/04 [ 11] Spin-Singlet Ground State in the Two-Dimensional Frustrated Triangular Lattice: YbAl3C3
Y. Kato, M. Kosaka, H. Nowatari, Y. Saiga, A. Yamada, T. Kobiyama, S. Katano, K. Ohoyama, H. S. Suzuki, N. Aso, and K. Iwasa
J. Phys. Soc. Jpn. 77 (2008) 053701.
[ 12] Structural Phase Transition in the Spin Gap System YbAl3C3
T. Matsumura, T. Inami, M. Kosaka, Y. Kato, T. Inukai, A. Ochiai, H. Nakao, Y. Murakami, S. Katano, and H. S. Suzuki
J. Phys. Soc. Jpn. 77 (2008) 103601.
[ 13] Analysis of 11B Powder Pattern Lineshape of MgB2 in the Normal Conductive Phase T. Yamaji, M. Murakami, J. Fukazawa, T. Shimizu, and K. Takegoshi
J. Phys. Soc. Japan, 77(4), 044711-1-4, 2008 [ 14] Fermi surface in BaNi2P2
T.Terashima, M.Kimata, H.satsukawa, A.Harada, K.Hazama, S.Uji, M.Imai, AIyo Hijiri, H.Kiyo, H.Eisaki, H. Harima JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN, 2009
[ 15] 27Al NMR/NQR studies of YbAl3C3
Takeshi Mito, Satoru Tomisawa, Shinji Wada, Hisatomo Harima, Kenjiro Hashi, Tadashi Shimizu, Atsushi Goto, Shinobu Ohki, Yoshiaki Kato and Masashi Kosaka
Journal of the Physical Society of Japan 78, No.1 (2009) 014709
[ 16] Sample size dependence of excess resistance near critical field in mesoscopic superconducting Al disk A. Harada, K. Enomoto, T. Yakabe, M. Kimata, K. Hazama, H. Satsukawa, T. Terashima, S. Uji Journal of Physics: Conference Series, 150 , 2009
[ 17] The new route process of V3Ga mono-cored and multifilamentary wires using high Ga content Cu-Ga compound and V matrix precursor
Y. Hishinuma, A. Kikuchi, Y. Iijima, T. Takeuchi and A. Nishimura Journal of physics: Conference Series, Vol.97, (2008), 012131
[ 18] Study of RHQT-processed Nb3Al Wires for High-Fied Accelerator Magnet Applications
C. Mitsuda, K. Tsuchiya, A. Terashima, A. Yamamoto, T. Takeuchi, N. Banno, S. Nimori, A. Kikuchi, Y. Iijima, K. Okamoto, T. Fukuda, K. Takenaka, T. Takao, K. Nakamura and K. Tagawa
Journal of Physics: Conference Series 97 (2008) 012059 [ 19] Pressure and magnetic field effect on transport gap of black SmS
K. Imura, K. Matsubayashi, H. S. Suzuki, K. Deguchi, N. K. Sato J. Phys.: Conf. Series , 121 , 2008
[ 20] Temperature dependence of the optical nuclear orientation in InP
Atsushi Goto, Seiichi Kato, Ivan Turkevych, Shinobu Ohki, Tadashi Shimizu, Kenjiro Hashi, Kanji Takehana, Tadashi Takamasu and Hidefumi Kitazawa
Journal of Physics: Conference Series 150 (2009) 022018 [ 21] Effects of Static Magnetic Field on Mutagenesis in in vitro
M. Ikehata, S. Yoshie, N. Hirota and T. Hayakawa Journal of Physics: Conference Series 156 (2009) 012015.
[ 22] Low-temperature magnetization of the low-dimensional magnet Cu3Mo2O9 under high magnetic fields T Hamasaki, H Kuroe, T Sekine, M Hase and H Kitazawa
J. Phys.: Conf. Ser. 150 (2009) 042047
[ 23] Anomalous pressure effect on the steplike magnetostriction of (La0.4Pr0.6)1.2Sr1.8Mn2O7, bilayered manganese oxide Y. Yamato, Y. Nakanishi, M. Matsukawa, T. Kumagai, R. Suryanarayanan, S. Nimori, M. Apostu, A. Revcolevschi, K. Koyama, N. Kobayashi
Journal of Physics. Conf. Ser. 150 (2009) 042121.
[ 24] Physical Properties of quasi-two dimensional organic conductors in strong magnetic fields S.Uji J.S.Brooks
The physics of organic superconductors and aonductors , Chapter 6 , 2008 [ 25] Magneto-Optical Properties of n-type Modulation-doped (Cd,Cr)Te Quantum Well
Takano, T. Nishizawa, J. W. Lee, S. Kuroda, Y. Imanaka, T. Takamasu, H. Akinaga PHYSICA E , Vol.40/ Page 1166-1168 , 2008年
[ 26] 11B Nuclear Magnetic Resonance Study on Existence of Boron-Hydrogen Complex in Boron-Doped Diamond M. Murakami, T. Shimizu, M. Tansho, Y. Takano, S. Ishii, E. Ekimov, V. Sidorov, H. Kawarada, and K. Takegoshi Jpn. J. Appl. Phys., 46(46), L1138-L1140, 2007
[ 27] Surface-sensitive NMR in optically pumped semiconductors Atsushi Goto, Tadashi Shimizu, Kenjiro Hashi, Shinobu Ohki,
Applied Physics A: Materials Science & Processing 93, No.2 (2008) 533-536 [ 28] Ac Susceptibility Studies of Spin Freezing Behavior in U2CuSi3
D. X. Li, S. Nimori, T. Yamamura , Y. Shiokawa J. Appl. Phys. 103 (2008) 07B715 1-3..
[ 29] High-field nuclear magnetic resonance with a newly designed hybrid magnet system
Kenjiro Hashi, Tadashi Shimizu, Teruaki Fujito, Atsushi Goto, Shinobu Ohki, Toshihisa Asano and Shigeki Nimori Japanese Journal of Applied Physics 48 (2009) 010220, Rapid Communication
[ 30] Colossal electroresistance and colossal magnetoresistive step in paramagnetic insulating phase of single crystalline bilayered manganite (La0.4Pr0.6)1.2Sr1.8Mn2O7
Y. Yamato, M. Matsukawa,Y. Murano, R. Suryanarayanan, S. Nimori, M. Apostu, A. Revcolevschi, K. Koyama, N. Kobayashi Applied Physics Letters, 94,092507 (2009)
[ 31] Volume dependence of the magnetic coupling in LaFe13-xSix based compounds
L. Jia, J. R. Sun, F. W. Wang, T. Y. Zhao, H. W. Zhang, B. G. Shen, D. X. Li, S. Nimori, Y. Ren, and Q.S. Zeng Appl. Phys.Lett. 92(2008) 101904 1-3
[ 32] Primitive description for hall oscillations in the extream quantum limit of (TMTSF) 2CI04 is siccussed in terms of Fermi surface nesting, whose stability strongly depends on magnetic field
S.McKernan , P.M .Chaikin , J.S. Brooks , S.Uji
SOLID STATE COMMUNICATIONS , Vol.145/No.7/p.385-p.388 , 2008
[ 33] Multifilamentary Nb-Zr and V-Ti superconducting alloys prepared by diffusion reaction between constituent pure-metal subeleme 竹内孝夫,瀧川博幸,中川正規,伴野信哉,井上廉,飯嶋安男,菊池章弘
SUPERCONDUCTOR SCIENCE & TECHNOLOGY, 21, 2, 025004-1-025004-8,(2008).
[ 34] Structural-microstructural characteristics and its correlations with the superconducting properties of in situ PIT-processed MgB2 tapes with ethyltoluene and SiC powder added
A.Anjana, A.Matsumoto, H.Kitaguchi, Y. Matsui, T.Hara, K.Watanabe, H.Yamada, N.Uchiyama, H.Kumakura Superconductor Science and Technology , Vol. 21 , 2008
[ 35] Superconducting properties of MgB2/Fe tape heavily doped with nanosized SiC A. Matsumoto, H. Kitaguchi, H. Kumakura
Superconductor Science and Technology , Vol. 21 , 2008
[ 36] Fabrication of high-performance MgB2 wires by an internal Mg diffusion process J.M.Hur, K.Togano, A.Matsumoto, H.Kumakura, H. Wada, M.Kimura
Superconductor Science and Technology , Vol. 21 , 2008
[ 37] Minimization of the hysteresis loss and low-field instability in technical Nb3Al conductors Banno, N., Takeuchi, T., Nimori, S., Tanaka, K., Nakagawa, K., Tsuchiya, K
Superconductor Science & Technology, vol. 21, no. 11, 115020 (7 pp.), 2008 [ 38] Cu Stabilized Nb3Al Strands for the High Field Accelerator Magnet
A. Kikuchi, R. Yamada, E. Barzi, M. Lamm, T. Takeuchi, D. Torrioni, A. Zlobin
IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY , p.p. 1026-1030 , Vol. 2008 [ 39] Structure and High-Field performance of New Nb3Sn Wires Fabricated from Sn-Based Alloys
K. Tachikawa, Y. Hayashi, K. Nakata, H. Sasaki, M.Yamaguchi and T. Takeuchi accepted for publication in IEEE Trans. Appl. Superconductivity, Vol.19 (June, 2009).
[ 40] Superconducting properties and microstructure of V3Ga multifilamentary wires through a PIT process using high Ga content compounds
Y. Hishinuma, A. Kikuchi, Y. Iijima, T. Takeuchi, H. Taniguchi, M. Tomonaga and A. Nishimura IEEE Transactions on Applied Superconductivity in press.
[ 41] Development of RHQT-Processed Nb3Al Wire for High-Field Accelerator Magnet Applications
K. Tsuchiya, C. Mitsuda, A. Terashima, A. Yamamoto, T. Takeuchi, N. Banno,S. Nimori, A. Kikuchi, Y. Iijima, K. Okamoto, T. Fukuda, K. Takenaka, T. Takao, K. Tagawa
IEEE Trans. Appl. Superconductivity, Vol.18, No. 2 (2008) pp. 1031-1034.
[ 42] Reduction of the matrix ratio for improvement of the non-Cu J(c) of Nb3Al wires N. Banno, T. Takeuchi, Y. Iijima and A. Kikuchi
IEEE Trans. Appl. Supercond., vol. 18, no. 2, pp. 1035-1038, 2008 [ 43] Status and perspective of the Nb3Al development
竹内孝夫, 菊池章弘, 伴野信哉, 北口仁, 飯嶋安男, 田川浩平, 中川和彦, 土屋清澄, 満田史織, 小泉徳潔, 奥野清 CRYOGENICS, 48, 7-8, 371-380, (2008)
[ 44] Fundamental studies for the application of quench protection systems based on an active power method for cryocooled LTS coils K. Takeuchi, N. Nanato, S. Murase, SeokBeom Kim, G. Nishijima, K. Watanabe, 竹内孝夫,伴野信哉,菊池章弘 CRYOGENICS, 48, 3-4, 148-153, (2008)
[ 45] Overview of Nb3Sn and V3Ga Conductor Development in Japan K. Tachikawa
Cryogenics, Vol.48 (2008) pp317-322.
[ 46] Structure and High-Field Performance of Jelly Roll Processed Nb3Sn Wires Using Sn-Ta and Sn-Ti Based Alloy Sheet K. Tachikawa, T. Tsuyuki, Y. Hayashi, K. Nakata and T. Takeuchi
Adv. Cryogenic Engineering (Materials), Vol.54 (2008) pp244-251.
[ 47] Mg2Cu化合物を添加源としたCu添加MgB2超伝導線材の高温領域における臨界電流特性
菱沼良光、菊池章弘、竹内孝夫、山田修一
低温工学(Journal of the Cryogenic Society of Japan), Vol.43, (2008), p.330-p.335.
[ 48] Nb3Al線材 竹内孝夫
電気学会技術報告書 先進超電導線材の製造技術と特性,1110,46-49,(2008)
[ 49] 超1GHz NMRマグネットを目指したBi-2223テープ線材の高磁場特性評価
長谷 隆司、財津 享司、濱田 衛、崔 世鎔、木吉 司
FSST NEWS （社）未踏科学技術協会 超伝導科学研究会 会誌 , Vol. 117 , 2008年
[ 50] Bi-2223テープ線材の高磁界特性技術の現状
長谷 隆司、財津 享司、濱田 衛、崔 世鎔、木吉 司
超電導Web21 （財）国際超電導産業技術研究センター , Vol. 4 , 2008年
[ 51] Simultaneous alignment and micropatterning of carbon nanotubes using modulated magnetic field 津田薫、目義雄
Science and Technology of Advanced materials , Vol. 10 , Received 30 June 2008, accepted for publication 2 7 October 2008, Published 22 May 2009
[ 52] Magnetic Orientation of Lamellar Microdomains in All-Amorphous Block Copolymer Bulk and Solutions S. Sakurai, A. Yasui, T. Kiyoshi, F. Kimura, T. Kimura
投稿中
[ 53] Magnetic Orientation of Cylindrical Microdomains in an Ultra-Thin Film of All-Amorphous Block Copolymers S. Sakurai, Y. Tsuji, A. Yasui, H. Masunaga, S. Sasaki, H. Okuda, T. Kiyoshi, M. Yamato, F. Kimura, T Kimura 投稿中
[ 54] High Field 17O Solid-State NMR Study of Alanine Tripeptides
K.Yamauchi, M. Okonogi, H. Kurosu, M. Tansho, T. Shimizu, T. Gullion, T. Asakura J. Magn. Reson. , Vol. 190 n 2008
[ 55] Effects of magnetic field on shape evolution of Fe-Co particles in a Cu matrix
Chiharu Kanno, Toshiyuki Fujii, Hideyuki Ohtsuka, Susumu Onaka and Masaharu Kato Philosophical Magazine, 89 [8], 747-759 (2009).
[ 56] Anisotropic elasticity of magnetically ordered agarose gel I. Yamamoto, S. Ozawa, T. Makino, M. Yamaguchi, T. Takamasu Sci. Tech. Adv. Mater. Vol. 9 (2008)
[ 57] Two-dimensional 11B–11B exchange NMR study in mesoporous boron carbon nitride at 21.8 T M. Murakami, T. Shimizu, M. Tansho, A. Vinu, K. Ariga, T. Mori, and K. Takegoshi
Solid State Nucl. Magn. Reson., 31(4), 193-196, 2007.
[ 58] Characterization of Boron-doped Diamonds Using 11B High-resolution NMR at High Magnetic Fields
M. Murakami, T. Shimizu, M. Tansho, Y. Takano, S. Ishii, E.A. Ekimov, V.A. Sidorov, H. Sumiya, H. Kawarada, and K. Takegoshi
Diamond and Related Materials, 17(11), 1835-1839, 2008
[ 59] The role of solutal convection in protein crystal growth-A new dimensionless number to evaluate the effects of convection on protein crystal growth
L.B. Wang, N.I. Wakayama, W.Q. Tao
Journal Crystal Growth：Vol.310、No.24、Page.5370～5374 , 2008/12 [ 60] - Uncertainties in crystallization of hen-egg white lysozyme: reproducibility issue
D.C.Yin, N.I. Wakayama, H.M. Lu, Y.J. Ye, H.S. Li, H.M. Luo1, Y. Inatomi Crystal Research and Technology Vol.43、No.4、Page.447～454 , 2008/4 [ 61] Growing and dissolving protein crystals in a levitated and containerless droplet
D.C. Yin, H.M. Lu, L.Q. Geng, Z.H. Shi, H.M. Luo, H.S. Li, Y.J.Ye, W.H. Guo, P.S. Shang and N.I. Wakayama Journal of Crystal Growth Vol.310、No.6、Page.1206～1212, 2008/3