SiO<sub>2</sub>表面改性对高填充SiO<sub>2</sub>/聚四氟乙烯复合薄膜性能的影响

周茜; 张瑶; 陈蓉; 沈佳斌; 郭少云

doi:10.13801/j.cnki.fhclxb.20191219.002

SiO₂表面改性对高填充SiO₂/聚四氟乙烯复合薄膜性能的影响

doi: 10.13801/j.cnki.fhclxb.20191219.002

四川大学　高分子材料工程国家重点实验室，成都 610065

基金项目: 国家自然科学基金创新研究群体科学基金(51721091)

详细信息

通讯作者:
陈蓉，博士，副研究员，硕士生导师，研究方向为氟塑料高性能化与功能化　E-mail：rongchen@scu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2019-10-30
- 录用日期: 2019-11-26
- 网络出版日期: 2019-12-19
- 刊出日期: 2020-09-15

Effect of surface modification of SiO₂ on properties of highly filled SiO₂/polytetrafluoroethylene composite films

State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China

摘要

摘要: 选用三种具有不同疏水官能团的硅烷偶联剂，即含苯基的偶联剂1(Ph-1)、含氟基的偶联剂2(F-2)和含环氧丙氧基的偶联剂3(GP-3)对SiO₂进行表面改性，并采用空气辅助干法共混、冷压烧结并车削成膜的方法制备了SiO₂填充量为35wt%、厚度为50 μm的SiO₂/聚四氟乙烯(PTFE)复合薄膜。改性后SiO₂在PTFE中分散均匀。研究了不同含量F-2对SiO₂/PTFE复合薄膜性能的影响，发现当含氟基的硅烷偶联剂F-2用量(与SiO₂质量比)为0.3%时，SiO₂/PTFE复合薄膜的针孔缺陷最少，拉伸强度由9.2 MPa提高至16.2 MPa；在10 GHz下，SiO₂/PTFE复合薄膜的介电常数由2.475降低至2.416，介电损耗由2.66×10⁻³降低至2.01×10⁻³，SiO₂/PTFE复合薄膜显示出优异的综合性能。
- 聚四氟乙烯 /
- SiO₂ /
- 硅烷偶联剂 /
- 介电性能 /
- 力学性能
Abstract: Three silane coupling agents with different hydrophobic groups, namely phenyl-containing coupling agent 1(Ph-1), fluorine-containing coupling agent 2(F-2) and a glycidoxy-containing coupling agent 3(GP-3) were used to modify SiO₂. The SiO₂/polytetrafluoroethylene(PTFE) composite films with 35wt% SiO₂ and thickness of 50 μm were prepared by air-assisted dry blending, cold-pressing, sintering and skiving techniques. The dispersion of SiO₂ throughout the PTFE matrix is uniform after the modification. The effects of F-2 contents on the properties of SiO₂/PTFE composite film were studied. The results show that when the content(mass ratio to SiO₂) of the coupling agent is 0.3%, the pinhole defects of SiO₂/PTFE composite film are rarely observed, and the tensile strength increases from 9.2 MPa to 16.2 MPa. Meanwhile, the dielectric constant decreases from 2.475 to 2.416 at 10 GHz, and the dielectric loss decreases from 2.66×10⁻³ to 2.01×10⁻³, exhibiting improved dielectric properties.
- polytetrafluoroethylene /
- SiO₂ /
- silane coupling agents /
- dielectric properties /
- mechanical properties

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图 1 SiO₂和不同偶联剂改性SiO₂的亲水接触角

Figure 1. Water contact angles of SiO₂ and different silanes treating SiO₂

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图 2 不同偶联剂改性前后SiO₂/聚四氟乙烯(PTFE)复合薄膜的SEM图像

Figure 2. SEM images of SiO₂/polytetrafluoroethylene(PTFE) composite films before and after treated by different silanes ((a) Pure SiO₂;(b) Ph-SiO₂; (c) F-SiO₂; (d) GP-SiO₂)

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图 3 不同偶联剂改性前后SiO₂/PTFE复合薄膜表面光学显微镜图像

Figure 3. Optical microscope images of SiO₂/PTFE composite films before and after treated by different silanes((a) Pure SiO₂; (b) Ph-SiO₂; (c) F-SiO₂; (d) GP-SiO₂)

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图 4 不同偶联剂改性前后SiO₂/PTFE复合薄膜的储能模量

Figure 4. Storage modulus of SiO₂/PTFE composite films before and after treated by different silanes

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图 5 不同偶联剂改性前后SiO₂/PTFE复合薄膜的力学性能

Figure 5. Mechanical properties of SiO₂/PTFE composite films before and after treated by different silanes

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图 6 不同偶联剂改性前后SiO₂/PTFE复合薄膜的介电性能

Figure 6. Dielectric properties of SiO₂/PTFE composite films before and after treated by different silanes

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图 7 F-2和不同含量F-2改性的SiO₂的FTIR图谱

Figure 7. FTIR spectra of F-2 and SiO₂ modified with different contents of F-2

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图 8 不同含量F-2改性的PTFE/SiO₂复合薄膜的SEM图像

Figure 8. SEM images of SiO₂/PTFE composite films modified with different contents of F-2 ((a) Pure SiO₂; (b) 0.3%; (c) 0.6%; (d) 0.9%; (e) 1.5%; (f) 2.1%)

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图 9 不同含量F-2改性的SiO₂/PTFE复合薄膜表面光学显微镜图像

Figure 9. Optical microscope images of SiO₂/PTFE composite films modified with different contents of F-2 ((a) Pure SiO₂; (b) 0.3%; (c) 0.6%;(d) 0.9%; (e) 1.5%; (f) 2.1%)

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图 10 偶联剂改性SiO₂对SiO₂/PTFE复合薄膜的作用机制

Figure 10. Mechanism of coupling agent modified SiO₂ on SiO₂/PTFE composite films

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表 1 硅烷偶联剂改性SiO₂的配比

Table 1. Contents of silane coupling agent modifying SiO₂

Name	Mass ratio to SiO₂/%
Name	Ph-1	GP-3	F-2
Ph-SiO₂	0.3	—	—
GP-SiO₂	—	0.3	—
F-SiO₂	—	0.3	—
	—	—	0.9
	—	—	1.5
	—	—	2.1

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表 2 不同F-2含量的SiO₂/PTFE复合薄膜的宏观性能数据

Table 2. Macroscopic performance data of SiO₂/PTFE composite films with different contents of F-2

Mass ratio of F-2 to SiO₂/%	Density/ (g·cm⁻³)	Water absorption/10⁻⁶	Tensile strength/MPa	Elongation at break/%	Dielectric constant	Dielectric loss/10⁻³
0	2.18	4.63±2.61	9.18±0.58	19.5±0.6	2.475	2.66
0.3	2.21	4.05±1.05	16.20±0.89	15.9±0.5	2.416	2.01
0.9	2.19	2.50±1.54	9.22±0.50	15.5±1.4	2.431	1.65
1.5	2.19	2.57±0.59	11.08±0.79	13.2±0.4	2.421	1.53
2.1	2.19	2.88±1.53	9.55±1.21	13.5±2.5	2.409	1.48

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