Structural evolution of fused silica below the glass-transition temperature revealed by in-situ neutron total scattering

Structural evolution of fused silica below the glass-transition temperature revealed by in-situ neutron total scattering
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原位中子全散射揭示了玻璃化转变温度以下熔融石英的结构演化

DOI:
10.1016/j.jnoncrysol.2019.119760
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发表时间:
2020
影响因子:
3.5
通讯作者:
Elliott, Stephen R.
Elliott, Stephen R.
中科院分区:
材料科学2区
文献类型:
--
作者:
Shi, Ying;Ma, Dong;Song, Albert P.;Wheaton, Bryan;Bauchy, Mathieu;Elliott, Stephen R.

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玻璃结构在室温下完全冻结的普遍看法在宏观和原子尺度上都受到了挑战。在这里,我们展示了一种分析方法,以阐明在低于玻璃化转变温度的温度下使用原位中子全散射的熔融石英(FS)的连续结构变化的细节。我们发现SiO4四面体在整个温度范围内膨胀,局部热膨胀系数为9.1 × 10−6K−1,而平均中程距离,由结构因子的第一个尖锐衍射峰得出,以21 × 10−6K−1的速率膨胀。这种膨胀差异反映了“刚性单元模式”模型内的玻璃结构变化,其中每个四面体表现为刚性单元,并且刚性单元之间的柔性旋转导致两倍以上的中程热膨胀。我们进一步证明,这种旋转改变了个别环的形状,导致第一个尖锐的衍射峰(FSDP)的可测量的变化。这项研究为测量其他硅酸盐玻璃的结构变化铺平了道路,特别是通过玻璃化转变。
The common belief that glass structure is completely frozen-in at room temperature is challenged at both macroscopic and atomic scales. Here, we demonstrate an analytical method to elucidate the fine details of a continuous structural change of fused silica (FS) at temperatures below the glass-transition temperature usingin-situneutron total scattering. We find that the SiO4tetrahedron expands through the entire temperature range with a local coefficient of thermal expansion of 9.1 × 10−6K−1, while the average medium-range distance, derived from the first sharp diffraction peak of the structure factor, expands at a rate of 21 × 10−6K−1. Such an expansion difference reflects glass-structure changes within the “rigid-unit mode” model, where each tetrahedron behaves as a rigid unit and the flexible rotations between rigid units lead to more than two times higher medium-range thermal expansion. We further demonstrate that such rotations change the shape of individual rings, leading to a measurable change in the first sharp diffraction peak (FSDP). This study paves the way to measure the structural changes of other silicate glasses, especially through the glass transition.
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