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通过魔角旋转证实高岭土中的核自旋-晶格弛豫机制

Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magic-angle spinning.

作者信息

Hayashi S, Akiba E

机构信息

National Institute of Materials and Chemical Research, Ibaraki, Japan.

出版信息

Solid State Nucl Magn Reson. 1995 Aug;4(6):331-40. doi: 10.1016/0926-2040(95)00005-b.

Abstract

Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in 1H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between 1H spins is strong. 29Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the 29Si relaxation of relatively pure samples under static and slow-spinning conditions. 27Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between 27Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated.

摘要

通过对高岭土样品进行魔角旋转(MAS),对其自旋 - 晶格弛豫机制进行了重新研究。MAS有助于区分弛豫机制:与电子自旋的偶极 - 偶极相互作用引起的直接弛豫速率不受旋转影响,而自旋扩散辅助的弛豫速率则受旋转影响。自旋扩散在1H弛豫中起主导作用。由于1H自旋之间的偶极耦合很强,MAS仅使弛豫行为发生轻微变化。在高于2 kHz的旋转条件下,29Si通过与电子自旋的偶极 - 偶极相互作用直接弛豫。在静态和慢旋转条件下,在相对纯净样品的29Si弛豫中已清楚观察到自旋扩散效应。27Al通过三种机制弛豫:声子耦合四极相互作用、自旋扩散以及与电子自旋的偶极 - 偶极相互作用。第一种机制占主导,而最后一种可忽略不计。在2.5 kHz的旋转速率下,27Al自旋之间的自旋扩散被完全抑制。我们从理论上分析了弛豫行为并进行了定量讨论。已估算出顺磁杂质的浓度、电子自旋 - 晶格弛豫时间和自旋扩散速率。

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