硅烷化多壁碳纳米管/硅橡胶复合材料的制备和介电性能

张子靖; 刘畅; 李如会; 吴崇刚; 龚兴厚; 胡涛

doi:10.13801/j.cnki.fhclxb.20191113.004

硅烷化多壁碳纳米管/硅橡胶复合材料的制备和介电性能

doi: 10.13801/j.cnki.fhclxb.20191113.004

湖北工业大学　材料与化学工程学院　绿色轻质材料与加工协同创新中心　绿色轻工材料湖北省重点实验室，武汉 430068

基金项目: 国家自然科学基金(51703053)；湖北省自然科学基金(2016CFB205)

详细信息

通讯作者:
胡涛，博士，讲师，硕士生导师，研究方向为有机硅功能材料及其衍生物　E-mail：hutao@mail.hbut.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2019-07-28
- 录用日期: 2019-10-12
- 网络出版日期: 2019-11-13
- 刊出日期: 2020-07-15

Preparation and dielectric properties of silanized multi-walled carbon nanotubes/silicone rubber composites

Hubei Provincial Key Laboratory of Green Materials for Light Industry, Collaborative Innovation Center of Green Light-weight Materials and Processing, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China

摘要

摘要: 采用三种不同官能度的硅烷偶联剂(甲基三乙氧基硅烷(MTES）、二甲基二乙氧基硅烷(DMDES)及三甲基乙氧基硅烷(TMES))在有水条件下对多壁碳纳米管(MWCNTs)进行表面改性，通过FTIR、XPS、TG及SEM表征了MWCNTs改性前和改性后的化学结构。采用机械共混法制备了MWCNTs/硅橡胶(SR)复合材料。SEM结果表明，将不同质量分数的MWCNTs、MWCNTs-MTES、MWCNTs-DMDES和MWCNTs-TMES填充到SR中，硅烷改性可以降低MWCNTs间的相互作用，改善其在SR中的分散性。拉伸试验结果表明，改性MWCNTs与SR之间的相互作用增强，二者的相容性得到改善。当改性MWCNTs含量≤2wt%时，MWCNTs/SR复合材料的弹性模量无明显变化。介电性能测试结果表明，当MWCNTs-MTES质量分数为2wt% 时，MWCNTs-MTES/SR复合材料在10⁴ Hz时介电常数达到5.02，较纯硅橡胶提高了57%，而介电损耗仍低于0.01，保持在极低水平。
- 硅烷偶联剂 /
- 多壁碳纳米管 /
- 硅橡胶 /
- 复合材料 /
- 介电性能
Abstract: The three different silane coupling agents (methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES) and trimethylethoxysilane (TMES)) were used to modify the surface of multi-walled carbon nanotubes (MWCNTs) under the hydrous conditions. The chemical structures of MWCNTs before and after modification were characterized by FTIR, XPS, TG and SEM. The different mass fractions of MWCNTs, MWCNTs-MTES, MWCNTs-DMDES and MWCNTs-TMES were filled in silicone rubber (SR). The MWCNTs/SR composites were prepared by mechanical blending. SEM images show that the silane modification can reduce the interaction between MWCNTs and improve their dispersion in SR. The tensile tests show that the interaction between MWCNTs and SR is enhanced and the compatibility between them is improved. The elastic modulus of the MWCNTs/SR composites shows no obvious change when the contents of modified MWCNTs are within 2wt%. The dielectric constant of MWCNTs/SR composite reaches 5.02 (at 10⁴ Hz) when filled with 2wt% modified MWCNTs-MTES, which is 57% higher than that of the pure SR, while the dielectric loss is still less than 0.01 (at 10⁴ Hz).
- silane coupling agents /
- multi-walled carbon nanotubes /
- silicone rubber /
- composites /
- dielectric properties

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图 1 MTES改性多壁碳纳米管(MWCNTs)的反应机制

Figure 1. Reaction mechanism of MTES modified multi-walled carbon nanotubes(MWCNTs)

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图 2 MWCNTs改性前后的FTIR图谱

Figure 2. FTIR spectra of MWCNTs before and after modification

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图 3 MWCNTs改性前后的XPS图谱

Figure 3. XPS spectra of MWCNTs before and after modification

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图 4 MWCNTs和MWCNTs-MTES的C 1s图谱

Figure 4. C 1s spectra of MWCNTs and MWCNTs-MTES

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图 5 MWCNTs改性前后的TG曲线

Figure 5. TG curves of MWCNTs before and after modification

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图 6 MWCNTs和MWCNTs-MTES的SEM图像

Figure 6. SEM images of MWCNTs and MWCNTs-MTES

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图 7 MWCNTs不同添加量的MWCNTs/SR、MWCNTs-MTES/SR、MWCNTs-DMDES/SR及MWCNTs-TMES/SR复合材料的SEM图像

Figure 7. SEM images of MWCNTs/SR, MWCNTs-MTES/SR, MWCNTs-DMDES/SR, MWCNTs-TMES/SR composites with different MWCNTs mass fractions

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图 8 不同MWCNTs添加量的MWCNTs/SR、MWCNTs-MTES/SR、MWCNTs-DMDES/SR和MWCNTs-TMES/SR复合材料的介电常数

Figure 8. Permittivities of MWCNTs/SR, MWCNTs-MTES/SR, MWCNTs-DMDES/SR and MWCNTs-TMES/SR composites with different MWCNTs mass fractions

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表 1 甲基三乙氧基硅烷(MTES）、二甲基二乙氧基硅烷(DMDES)及三甲基乙氧基硅烷(TMES)硅烷偶联剂的官能度

Table 1. Functionality of methyltriethoxysilane(MTES), dimethyldiethoxysilane(DMDES) and trimethylethoxysilane(TMES) sliane coupling agents

Sliane coupling agent	Functionality
MTES	3
DMDES	2
TMES	1

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表 2 MWCNTs和MWCNTs-MTES的主要元素及含量

Table 2. Summary of element compositions of MWCNTs and MWCNTs-MTES

Core level	MWCNTs		MWCNTs-MTES
Core level	Peak/eV	Content/at%	Peak/eV	Content/at%
C 1s	254.05	96.25	284.94	53.64
O1s	532.94	3.75	532.94	30.95
Si 2p	−	−	102.98	15.41

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表 3 MWCNTs和MWCNTs-MTES的C 1s结合方式及含量

Table 3. C 1s peak affiliations and contents of MWCNTs and MWCNTs-MTES

Core level	MWCNTs		MWCNTs‒MTES
Core level	Peak/eV	Atm/at%	Peak/eV	Atm/at%
sp² C=C	284.62	58.90	284.59	40.01
sp³ C—C	285.48	16.67	285.21	53.59
C—O	286.79	7.62	287.60	4.09
O=C—O	288.32	3.37	−	−
π-π* C	291.02	13.44	290.25	2.31

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表 4 MWCNTs/SR、MWCNTs-MTES/SR、MWCNTs-DMDES/SR及MWCNTs-TMES/SR复合材料的拉伸性能

Table 4. Tensile properties of MWCNTs/SR, MWCNTs-MTES/SR, MWCNTs-DMDES/SR and MWCNTs-TMES/SR composites

Sample	Mass fraction of MWCNTs/wt%	Tensile strength/MPa	Elongation at break/%	Young’s modulus/MPa
Pure SR	−	0.26	408	0.12
MWCNTs/SR	0.5	0.23	348	0.15
	1.0	0.19	288	0.12
	1.5	0.17	248	0.14
	2.0	0.19	361	0.12
MWCNTs-MTES/SR	0.5	0.20	204	0.15
	1.0	0.25	308	0.15
	1.5	0.23	304	0.14
	2.0	0.27	354	0.14
MWCNTs-DMDES/SR	0.5	0.23	294	0.16
	1.0	0.21	251	0.15
	1.5	0.20	228	0.16
	2.0	0.19	301	0.13
MWCNTs-TMES/SR	0.5	0.17	208	0.14
	1.0	0.18	218	0.14
	1.5	0.17	244	0.13
	2.0	0.16	291	0.11

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表 5 MWCNTs/SR、MWCNTs-MTES/SR、MWCNTs-DMDES/SR和MWCNTs-TMES/SR复合材料在10⁴ Hz的介电常数及介电损耗

Table 5. Permittivities and dielectric losses of MWCNTs/SR, MWCNTs-MTES/SR, MWCNTs-DMDES/SR and MWCNTs-TMES/SR composites at 10⁴ Hz

Sample	Mass fraction of MWCNTs/wt%	Permittivity	Dielectric loss/10⁻³
Pure SR	−	3.19	0.87
MWCNTs/SR	1.0	4.01	0.99
MWCNTs/SR	2.0	4.60	1.75
MWCNTs-MTES/SR	1.0	4.35	0.98
MWCNTs-MTES/SR	2.0	5.02	1.02
MWCNTs-DMDES/SR	1.0	4.07	1.21
MWCNTs-DMDES/SR	2.0	4.77	1.92
MWCNTs-TMES/SR	1.0	4.18	0.83
MWCNTs-TMES/SR	2.0	4.42	1.42

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