硅油的高压拉曼散射

doi:10.7503/cjcu20140541

摘要/Abstract

摘要：

利用金刚石对顶砧高压实验技术及红宝石荧光标压方法, 研究了3种不同黏度的硅油(Silicone oil AP 150 wacker, Baysilone oil M1000和Baysilone oil M30000)在室温条件下的高压拉曼散射光谱, 实验最高压力为20 GPa. 获得了硅油的不同拉曼振动模式在高压下的变化规律, 发现Baysilone oil M1000和Baysilone oil M30000分别在0.47和0.31 GPa压力下发生分子结构或构型转变, 使Si—O伸缩振动拉曼信号强度降低, 并产生新的拉曼振动信号; Silicone oil AP 150 wacker, Baysilone oil M1000和Baysilone oil M30000分别在9, 8和4.5 GPa压力下出现振动模式消失或振动频率随压力变化的斜率发生改变, 表明具有不同结构和黏度的硅油在不同压力下内部结构发生了变化.

关键词: 高压, 拉曼散射, 金刚石对顶砧, 硅油, 拉曼振动模式

Abstract:

The Raman spectra of silicone oil with different viscosities(Silicone oil AP 150 wacker, Baysilone oil M1000 and Baysilone oil M30000) as a function of pressure up to 20 GPa were investigated in a diamond anvil cell. The pressure dependence of Raman vibrations of these silicone oils were obtained and analyzed. The results indicated that the molecular structure or configuration of Baysilone oil M1000 changes at 0.47 GPa and that of Baysilone oil M30000 changes at 0.31 GPa, respectively. This is confirmed by the decrease of the intensity of the Si—O stretch vibration and the emerging of novel vibrations at the corresponding solidification point. In addition, it was found that the pressure dependence of the vibrational frequencies changes and some vibrational modes disappear at 10, 8 and 4.5 GPa for Silicone oil AP 150 wacker, Baysilone oil M1000 and Baysilone oil M30000, respectively, indicating the inherent structural change of these silicone oils.

Key words: High pressure, Raman scattering, Diamond anvil cell, Silicone oil, Raman vibrational mode

中图分类号:

TrendMD:

王晓霞, 李志慧, 陈晨, 王凯, 韩博, 周强, 李芳菲. 硅油的高压拉曼散射. 高等学校化学学报, 2014, 35(11): 2384.

WANG Xiaoxia, LI Zhihui, CHEN Chen, WANG Kai, HAN Bo, ZHOU Qiang, LI Fangfei. High Pressure Raman Spectra of Silicone Oil^†. Chem. J. Chinese Universities, 2014, 35(11): 2384.

图/表 7

Fig.1 Raman spectra of Silicone oil AP 150 wacker at room temperature and different pressures

Table 1 Raman vibrational mode assignments for Silicone oil AP 150 wacker at room temperature and pressure

$ν ˙$ /cm^-1	Vibrational mode	$ν ˙$ /cm^-1	Vibrational mode
410.6	SiC₂ bending	1029.4	Aromatic C—H out-of-plane bending
480.4	Si—O stretch	1124.6	Aromatic C—H out-of-plane bending
534.1	C—Si stretch	1156.8	Aromatic C—H out-of-plane bending
618.0	C—Si stretch	1190.9	Aromatic C—H out-of-plane bending
695.5	SiC₂ symmetric stretch	1568.0	Aromatic C—C stretch
728.3	SiC₂ antisymmetric stretch	1591.4	Aromatic C—C stretch
754.2	CH₃ rocking	2902.7	CH₃ symmetric stretch
986.1	Aromatic C—H out-of-plane bending	2965.6	CH₃ antisymmetric stretch
998.3	Aromatic C—H out-of-plane bending	3050.6	Aromatic C—H stretch

Table 1 Raman vibrational mode assignments for Silicone oil AP 150 wacker at room temperature and pressure

$ν ˙$ /cm^-1	Vibrational mode	$ν ˙$ /cm^-1	Vibrational mode
410.6	SiC₂ bending	1029.4	Aromatic C—H out-of-plane bending
480.4	Si—O stretch	1124.6	Aromatic C—H out-of-plane bending
534.1	C—Si stretch	1156.8	Aromatic C—H out-of-plane bending
618.0	C—Si stretch	1190.9	Aromatic C—H out-of-plane bending
695.5	SiC₂ symmetric stretch	1568.0	Aromatic C—C stretch
728.3	SiC₂ antisymmetric stretch	1591.4	Aromatic C—C stretch
754.2	CH₃ rocking	2902.7	CH₃ symmetric stretch
986.1	Aromatic C—H out-of-plane bending	2965.6	CH₃ antisymmetric stretch
998.3	Aromatic C—H out-of-plane bending	3050.6	Aromatic C—H stretch

Fig.2 Raman shift as a function of pressure for Silicone oil AP 150 wacker at room temperature (A) 400—1100 cm-1. a. SiC2 bending; .b Si—O stretch; c, d. C—Si stretch; e, f. SiC2 stretch; g. CH3 rocking; h—j. aromatic C—H out-of-plane bending.(B) 800—3100 cm-1. a—c. aromatic C—H out-of-plane bending; d, e. aromatic C—C stretch; f, g. CH3 stretch; h. aromatic C—H stretch.

Fig.3 Raman spectra at different pressures(A), Raman shift as a function of pressure(B) and microseope image(C) for Baysilone oil M1000 at room temperature a. C—Si—O bending; b. CH3 torsions/SiC2 deformation/rock/twist; c—e. Si—O stretch; f, g. SiC2 stretch; h, i. CH3 rocking; j, k. CH3 stretch; (C) photo of the Baysilone oil M1000 in sample chamber at 0.3 GPa.

Table 2 Raman vibrational mode assignments for Baysilone oil M1000 and Baysilone oil M30000 at room temperature and atmospheric pressure

Vibrational mode	$ν ˙$ /cm^-1		Vibrational mode	$ν ˙$ /cm^-1
Vibrational mode	Baysilone oil M1000	Baysilone oil M30000	Vibrational mode	Baysilone oil M1000	Baysilone oil M30000
C—Si—O bending	152.6	157.4	SiC₂ antisymmetric stretch	707.2	709.5
CH₃ torsions/SiC₂ defor-	190.0	193.4	CH₃ rocking	789.7	791.1
mation/rock/twist			CH₃ rocking	868.6	876.5
Si—O stretch	489.5	491.5	CH₃ symmetric stretch	2903.3	2904.2
SiC₂ symmetric stretch	686.7	688.3	CH₃ antisymmetric stretch	2964.2	2965.8

Table 2 Raman vibrational mode assignments for Baysilone oil M1000 and Baysilone oil M30000 at room temperature and atmospheric pressure

Vibrational mode	$ν ˙$ /cm^-1		Vibrational mode	$ν ˙$ /cm^-1
Vibrational mode	Baysilone oil M1000	Baysilone oil M30000	Vibrational mode	Baysilone oil M1000	Baysilone oil M30000
C—Si—O bending	152.6	157.4	SiC₂ antisymmetric stretch	707.2	709.5
CH₃ torsions/SiC₂ defor-	190.0	193.4	CH₃ rocking	789.7	791.1
mation/rock/twist			CH₃ rocking	868.6	876.5
Si—O stretch	489.5	491.5	CH₃ symmetric stretch	2903.3	2904.2
SiC₂ symmetric stretch	686.7	688.3	CH₃ antisymmetric stretch	2964.2	2965.8

Fig.4 Raman spectra at different pressures(A) and Raman shift as a function of pressure(B) for Baysilone oil M30000 at room temperature a. C—Si—O bending; b, c. CH3 torsions/SiC2 deformation/rock/twist; d. newly emerged vibration after 0.31 GPa; e—g. Si—O stretch; h, i. SiC2 stretch; j. CH3 rocking; k, l. CH3 stretch.

Fig.5 Pressure dependence of full width at half maximum(FWHM) of C—H stretch vibrations for Baysilone oil M1000(A) and Baysilone oil M30000(B) at room temperature ■ CH3 symmetric stretch; ● CH3 antisymmetric stretch.

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