羟碳铈矿的高压拉曼光谱研究

宋海鹏; 刘云贵; 李想; 靳树宇; 王欣宇; 巫翔

doi:10.11858/gywlxb.20190847

羟碳铈矿的高压拉曼光谱研究

doi: 10.11858/gywlxb.20190847

宋海鹏^1,,
刘云贵^{1, 2},
李想¹,
靳树宇¹,
王欣宇¹,
巫翔^1,*, ,

1.
中国地质大学地质过程与矿产资源国家重点实验室，湖北武汉　430074
2.
河北地质大学宝石与材料工艺学院，河北石家庄　050031

基金项目: 国家自然科学基金（41827802）

详细信息

作者简介:
宋海鹏（1995－），男，硕士研究生，主要从事高压矿物物理研究. E-mail: songhaipeng@cug.edu.cn

通讯作者:
巫　翔（1978－），男，博士，教授，主要从事地球深部物质的组成、状态和物性研究.E-mail: wuxiang@cug.edu.cn

中图分类号: O521.2; P574.1
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出版历程
- 收稿日期: 2019-10-16
- 修回日期: 2019-11-04

High-Pressure Raman Spectroscopic Study of Hydroxylbastnäsite-(Ce)

SONG Haipeng^1
,,
LIU Yungui^{1, 2},
LI Xiang¹,
JIN Shuyu¹,
WANG Xinyu¹,
WU Xiang^{1,*
, ,}

1.
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
2.
College of Gems and Materials Technology, Hebei GEO University, Shijiazhuang 050031, China

摘要

摘要: 羟碳铈矿是一种重要的含水稀土氟碳酸盐矿物，了解其高压下的物理性质对于探讨氟和水的存在对碳酸盐矿物物性的影响具有重要意义。运用金刚石压腔（DAC）技术与激光拉曼光谱，在室温下原位开展了羟碳铈矿的高压拉曼光谱学研究。结果显示，在常压下由[CO₃]^2–振动引起的拉曼峰共有6条：面内弯曲振动引起的拉曼峰位于604、742 cm^–1，对称伸缩振动引起的拉曼峰位于1 083、1 096和1 103 cm^–1，而1 430 cm^–1属于非对称伸缩振动；由[OH]^–振动引起的拉曼峰有6条，分别位于3 174、3 197、3 290、3 345、3 526和3 648 cm^–1。随着压力的增加（0～30 GPa），未发现拉曼峰的消失或新拉曼峰的出现，表明在测试压力范围内羟碳铈矿未发生相变。拉曼峰均往高波数偏移，其位移与压力呈现良好的线性正相关关系，由[CO₃]^2–的面内弯曲振动引起的拉曼峰对压力的依赖系数最小，为2(0.06) cm^–1/GPa，而基团外振动引起的拉曼峰对压力的依赖系数最大，为4.2(0.11) cm^–1/GPa。对比无水碳酸盐高压下拉曼峰的位移，认为[OH]^–和F^–的存在导致羟碳铈矿高压下结构中[CO₃]^2–基团的振动模式对压力的依赖性发生变化，进一步影响到晶体高压下的各向异性。这为研究地球深部碳酸盐的高压物性行为提供了新的启示。
- 羟碳铈矿 /
- 含水稀土氟碳酸盐 /
- 金刚石压腔 /
- 拉曼光谱
Abstract: Understanding the physical properties under high pressure of hydroxylbastnäsite-(Ce), an important hydrous rare earth element (REE) fluorocarbonate mineral, can provide key information to explore the effect of fluorine and hydroxyl on high-pressure behavior of carbonate minerals. Here Raman spectroscopy combined with diamond anvil cell (DAC) technology was employed to investigate the high-pressure properties of hydroxylbastnäsite-(Ce). At ambient conditions, the in-plane vibration bands of [CO₃]^2– are observed at 604 cm^–1 and 742 cm^–1, the symmetrical stretching bands are at 1 083, 1 096, and 1 103 cm^–1, and the asymmetric stretching vibration is at 1 430 cm^–1. Six vibration peaks of [OH]^– are at 3 174, 3 197, 3 290, 3 345, 3 526 and 3 648 cm^–1, respectively. The observation of three discrete [CO₃]^2– symmetrical stretching bands, instead of one, indicates that there may be at least three structurally-nonequivalent [CO₃]^2– groups in the hydroxyl-bästnasite-(Ce) structure. On compression, all of the Raman peaks show a continuous shift to the higher frequency and no new peaks appear, suggesting that no phase transition occurs up to 30 GPa at room temperature. The slope of the in-plane bending vibration of [CO₃]^2– is the smallest, about 2(0.06) cm^–1/GPa. Compared with the anhydrous carbonate, it can be inferred that the [OH]^– and F^– in the structures of hydroxylbastnäsite-(Ce) lead to the compression anisotropy. Our results provide new clues for studying the high-pressure physical behavior of carbonates in the deep earth.
- hydroxylbastnäsite-(Ce) /
- hydrous rare earth element (REE) fluorocarbonate mineral /
- diamond anvil cell /
- Raman spectroscopy

HTML全文

图 1 羟碳铈矿常压拉曼光谱（蓝色实线代表RRUFF数据库中羟碳铈矿的数据^[12]，红色实线代表本实验测得的羟碳铈矿数据，黑色实线代表氟碳铈矿的数据。）

Figure 1. Raman spectra of hydroxylbastnäsite-(Ce) at ambient conditions (The solid blue line represents the data for the hydroxylbastnäsite-(Ce) in the RRUFF database^[12]; the solid red line represents the hydroxylbastnäsite-(Ce) data measured in this experimental sample; the solid black line represents the data for bastnäsite.)

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图 2 高压下羟碳铈矿的代表性拉曼光谱（压力范围0～30 GPa）

Figure 2. Selected Raman spectra of hydroxylbastnäsite-(Ce) at high pressure (Pressure range is 0–30 GPa.)

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图 3 羟碳铈矿的拉曼振动频率随压力的变化（ν_i代表不同的拉曼振动峰）

Figure 3. Variations of Raman frequencies as a function of pressure (ν_i represents different Raman vibration peaks.)

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图 4 碳酸盐矿物中[CO₃]^2–的dν_i/dp（空心符号代表常见的几种无水碳酸盐，实心符号代表含水碳酸盐，*代表本次实验数据）

Figure 4. dν_i/dp of [CO₃]^2– in carbonate minerals (The open symbols represent several common anhydrous carbonates, the solid symbols represent aqueous carbonates, and * represents the experimental data.)

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表 1 常见稀土氟碳酸盐矿物常压拉曼峰

Table 1. Atmospheric pressure Raman peaks of common rare earth fluorocarbonate minerals

Mineral	Chemical formula	Raman peak/cm^–1
Mineral	Chemical formula	[CO₃]^2–				[OH]^–
Cordylite^[13]	Ce₂Ba[CO₃]₃F₂	720	967	1 088	1 538
Cordylite^[13]	Ce₂Ba[CO₃]₃F₂	628
Bastnäsite^[13]	Ce[CO₃]F	732	835	1 098	1 476
Bastnäsite^[13]	Ce[CO₃]F				1 447
Hydroxylbastnäsite-(Ce)^[12]	Ce[CO₃][(OH)_0.65F_0.35]			1 080		3 235
				1 087		3 493
				1 098		3 568
						3 638
Hydroxylbastnäsite-(Ce)^[14]	Ce[CO₃][(OH)_0.85F_0.15]	726	879	1 079	1 390	3 491
				1 097	1 425	3 564
						3 630
						3 648
Hydroxylbastnäsite-(Ce)*	Ce[CO₃][(OH)_0.62F_0.38]	604		1 083	1 430	3 174
		742		1 096		3 200
				1 103		3 290
						3 345
						3 526
						3 648
Note: * represents the experimental data.

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表 2 不同压力下羟碳铈矿拉曼峰峰位

Table 2. Raman peaks position of hydroxylbastnäsite-(Ce) under different pressures

Pressure/GPa	Raman peak/cm^–1
Pressure/GPa	REE-O/F				[CO]₃^2–				[OH]^–
0.7	168.7	262.2	357.8	411.4	742.2	1 084.8	1 093.7		3 169.7
1.2	166.2	263.6	360.1	408.9	741.9	1 084.8	1 095.9	1 102.7	3 172.8
2.0	168.1	272.7	363.5	410.0	741.4	1 087.0	1 098.2	1 104.9	3 172.1
3.3	171.7	279.6	368.9	416.6	745.1	1 089.2	1 102.6	1 109.2	3 176.9
4.7	174.3	285.1	375.8	420.4	744.6	1 093.7	1 107.1	1 113.6	3 177.9
5.8	177.5	292.3	380.4	427.2	749.9	1 097.1	1 111.5	1 118.2
6.2	180.4	295.3	383.8	429.5	751.6	1 098.2	1 111.5		3 179.4
7.5	182.7	300.8	385.4	433.9	754.1	1 100.4	1 114.9	1 122.7	3 179.1
9.6	187.8	312.0	401.9	445.6	763.6	1 107.1	1 122.7	1 129.4	3 181.7
10.9	190.5	315.9	404.6	448.4	760.9	1 109.3	1 124.9	1 131.4	3 183.4
11.5	196.8	321.4	410.6	455.5	764.5	1 113.8	1 128.4	1 135.5	3 183.5
13.5	201.7	326.6	413.6	459.8	769.0	1 116.0	1 131.6	1 137.9	3 185.8
14.0	199.2	329.7	417.9	466.3	766.2	1 118.2	1 134.7	1 142.4	3 187.0
16.0	205.7	339.7	424.9	476.0	768.6	1 125.9	1 140.4	1 149.1	3 187.2
18.0	209.9	344.7	430.1	479.6	777.0	1 129.3	1 144.9		3 189.9
18.6	205.8	349.6	433.5	484.2	776.9	1 130.4	1 146.0		3 192.4
20.1	214.9	354.7	438.2	489.3	778.8	1 133.8	1 149.3		3 189.7
22.0	214.6	359.0	443.3	490.9	783.4	1 136.0	1 151.5		3 190.4
23.1	219.0	360.4	446.1	499.4	781.6	1 138.2	1 156.0	1 164.8	3 192.5
24.0	223.3	364.5	448.2	502.2	791.0	1 142.7	1 158.2	1 169.2	3 192.7
25.7	228.3	368.0	451.6	506.7	789.0	1 144.9	1 160.4	1 173.6	3 192.8
27.0	240.2	376.9	474.8	519.2		1 151.1	1 164.8		3 193.6
28.8	235.5	380.2				1 151.5	1 168.1
30.0	238.9	391.0				1 153.7	1 172.8

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表 3 不同拉曼峰的压力依赖系数及误差

Table 3. Pressure dependence coefficients and errors for different Raman peaks

Raman peaks/cm^–1	Dependence coefficients/(cm^–1·GPa^–1)	Error	Raman peaks/cm^–1	Dependence coefficients/(cm^–1·GPa^–1)	Error
169	2.5	0.06	1 083	2.5	0.04
262	4.2	0.10	1 096	2.6	0.05
358	4.0	0.11	1 103	2.9	0.05
404	4.2	0.07	3 174	0.8	0.05
742	2.0	0.07	3 197	1.7	0.12

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