高压剪切作用下三水铝石的结构稳定性

姜昌国; 谭大勇; 谢亚飞; 罗兴丽; 肖万生

doi:10.11858/gywlxb.20210766

高压剪切作用下三水铝石的结构稳定性

doi: 10.11858/gywlxb.20210766

姜昌国^{1, 2, 3, 4,},
谭大勇^{1, 2, 3,*, ,},
谢亚飞^{1, 2, 3, 4},
罗兴丽^{1, 2, 3, 4},
肖万生^{1, 2, 3}

1.
中国科学院广州地球化学研究所矿物学与成矿学重点实验室, 广东广州　510640
2.
广东省矿物物理与材料研究开发重点实验室, 广东广州　510640
3.
中国科学院深地科学卓越创新中心, 广东广州　510640
4.
中国科学院大学, 北京　100049

基金项目: 国家自然科学基金（41372047，41572030）；中国科学院战略性先导科技专项（B类）（XDB18000000）

详细信息

作者简介:
姜昌国（1996－），男，硕士研究生，主要从事高压矿物学研究. E-mail：jiangchangguo@gig.ac.cn

通讯作者:
谭大勇（1975－），男，博士，副研究员，主要从事高压矿物学研究. E-mail：dytan04@gig.ac.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2021-04-07
- 修回日期: 2021-04-13
- 录用日期: 2021-04-29

Investigation on Structural Stability of $\gamma $-Al(OH)₃ under High Pressure and Shear Stress

JIANG Changguo^{1, 2, 3, 4
,},
TAN Dayong^{1, 2, 3,*
, ,},
XIE Yafei^{1, 2, 3, 4},
LUO Xingli^{1, 2, 3, 4},
XIAO Wansheng^{1, 2, 3}

1.
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
2.
Key Laboratory of Guangdong Province for Mineral Physics and Materials, Guangzhou 510640, Guangdong, China
3.
CAS Center for Excellence in Deep Earth Science, Guangzhou, 510640, Guangdong, China
4.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 利用旋转式金刚石对顶砧压机（RDAC）结合显微激光拉曼光谱和微区X射线衍射，研究了三水铝石（$\gamma $-Al(OH)₃）在高压剪切作用下的结构稳定性。常温加压至1.5 GPa，旋转180°后，$\gamma $-Al(OH)₃的结构开始转变。初始样品在高波数段的4个羟基伸缩振动峰（3 363、3 434、3 524和3 618 cm⁻¹）相继消失，出现3 303和3 560 cm⁻¹ 2个新峰。低波数段拉曼谱强度明显减弱，无非晶态宽峰；Al-O-Al变形振动双峰（568、539 cm⁻¹）和Al-O伸缩振动肩峰（321和307 cm⁻¹）分别融合为一个振动峰；4个羟基变形振动峰（1 052、1 018、981和922 cm⁻¹）仍然可见。继续加压至3.5 GPa，旋转360°后卸至常压，高波数段新出现的两个羟基伸缩振动峰、原Al-O-Al变形振动峰和Al-O伸缩振动峰仍然可见。对比准静水压条件下$\gamma $-Al(OH)₃高压相的拉曼谱和相转变压力（约2.7 GPa），认为常温高压剪切作用下$\gamma $-Al(OH)₃脱羟基生成了H₂O和${\rm{H}}_3{\rm{O}}_2^- $。卸压样品微区的X射线衍射谱进一步揭示，在高压剪切作用下，$\gamma $-Al(OH)₃的(OH)-Al-(OH)配位八面体骨架被破坏，沿c轴方向原子叠加的层间距缩小，对称性增强。这种不同于准静水压实验的结构改变来自腔体内压力的不均匀分布（0.5～4.5 GPa）。高压剪切作用下，三水铝石的结构稳定性研究对查明板块冷俯冲带中含水矿物的稳定性，推演俯冲板片的物理化学性质以及板块俯冲的速率具有重要意义。
- $\gamma $-Al(OH)₃ /
- 旋转式金刚石对顶砧压机 /
- 剪切应力 /
- 结构稳定性 /
- 拉曼光谱
Abstract: The structural stability of gibbsite $\gamma $-Al(OH)₃ was investigated under high pressure and shear stress conditions by using a rotating diamond anvil cell (RDAC) combining with micro-laser Raman spectroscopy and micro-beam X-ray diffraction. As increasing pressure to 1.5 GPa and rotating to 180°, gibbsite triggers a new structural change at room temperature. In the range of high-wavenumbers, the four peaks of hydroxyl vibration (3363, 3434, 3524 and 3618 cm⁻¹) disappear gradually, and two new peaks with different intensities appear at 3303 and 3560 cm⁻¹. In the range of low-wavenumbers, the intensities of Raman spectra are getting weaker and weaker, but the broad peaks of amorphism are not observed. Both of the double peaks (568, 539 cm⁻¹) of Al-O-Al deformation vibration and the shoulder peaks (321 and 307 cm⁻¹) of Al-O stretching vibration merge into one peak, respectively. However, the four vibration peaks of hydroxyl deformation vibration (1052, 1018, 981 and 922 cm⁻¹) still remain. In addition, further increasing pressure to 3.5 GPa and rotating to 360°, and finally decreasing to ambient pressure, two new peaks of hydroxyl stretching vibration in high-wavenumbers, and the peaks of Al-O-Al deformation vibration and Al-O stretching vibration in low-wavenumbers are still observed. Compared to the phase transition of $\gamma $-Al(OH)₃ under quasi-hydrostatic pressure conditions, the Raman spectra and phase transition pressure in this study reveal that the $\gamma $-Al(OH)₃ take place another new structure change under high pressure and shear stress conditions. The micro-beam X-ray diffraction spectrum of the quenched product reveals that the framework of (OH)-Al-(OH) octahedra of this new phase is still remain, but has a shorter distance between the layers of (OH)-Al-(OH) and a higher symmetry. This newfound structure change of gibbsite in this study mainly due to the inhomogeneous pressure distribution in the sample chamber (from 0.5 to 4.5 GPa). The investigation on structural stability of $\gamma $-Al(OH)₃ under high pressure and shear stress conditions is vital for us to identify the stability of hydrous minerals in the cold subduction slabs, and to derive the physical and chemical properties of slab and its subduction rates.
- $\gamma $-Al(OH)₃ /
- rotating diamond anvil cell /
- shear stress /
- structural stability /
- Raman spectra

HTML全文

图 1 $\gamma$-Al(OH)₃ 的晶体结构（绿色键为层内羟基，黄色键为层间羟基）

Figure 1. Crystal structure of $\gamma $-Al(OH)₃ (The green binding is intralayer OH, and the yellow binding is interlayer OH.)

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图 2 RDAC及其工作原理

Figure 2. Rotating diamond anvil cell and its operating principle

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图 3 高压剪切作用下$\gamma $-Al(OH)₃在2 800～4 800 cm⁻¹高波数段的代表性拉曼光谱

Figure 3. Representative Raman spectra of $\gamma $-Al(OH)₃ in the range of 2 800−4 800 cm⁻¹under high pressure and shear stress

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图 4 高压剪切作用下$\gamma $-Al(OH)₃在100～1 100 cm⁻¹低波数段的代表性拉曼光谱

Figure 4. Representative Raman spectra of $\gamma $-Al(OH)₃ in the range of 100−1 100 cm⁻¹ under high pressure and shear stress

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图 5 准静水压作用下$\gamma$-Al(OH)₃的代表性拉曼光谱

Figure 5. Representative Raman spectra of $\gamma $-Al(OH)₃ under quasi-hydrostatic pressure

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图 6 高压剪切作用前后样品的X射线衍射谱及其晶体结构指认

Figure 6. X-ray diffraction spectra of starting material and quenched product and the index of crystal structure

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图 7 高压剪切实验腔体内的压力分布和测试点的数字、图形标识(a)，测试点分布(b)，腔体内显微图片(c)

Figure 7. (a) Pressure distribution of sample chamber under high pressure and shear stress, and marks of measurement point; (b) distribution of measurement point; (c) microscopic image of sample

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