硫化体系对硅橡胶热老化性能的影响

范在乾; 咸日常; 边继辉; 葛旺泉; 邢雅雯; 孙丰睿

doi:10.13801/j.cnki.fhclxb.20230814.004

硫化体系对硅橡胶热老化性能的影响

doi: 10.13801/j.cnki.fhclxb.20230814.004

1.
山东理工大学　电气与电子工程学院，淄博 255049
2.
山东七星电气科技发展有限公司，淄博 255000

基金项目: 校城融合发展计划项目(2021JSCG0009)

详细信息

通讯作者:
咸日常，硕士，教授，博士生导师，研究方向为电气设备在线监测与故障诊断技术　E-mail: xianrc@163.com

中图分类号: TM215；TB332
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出版历程
- 收稿日期: 2023-05-24
- 修回日期: 2023-07-20
- 录用日期: 2023-07-29
- 网络出版日期: 2023-08-14
- 刊出日期: 2024-03-01

Effect of vulcanization system on thermal aging property of silicone rubber

1.
School of Electrical and Electronic Engineering, Shandong University of Technology, Zibo 255049, China
2.
Shandong Qixing Electric Technology Development CO., LTD., Zibo 255000, China

Funds: School City Integration Development Plan Project (2021JSCG0009)

摘要

摘要: 为了探究不同硫化体系对电缆附件增强绝缘用硅橡胶热老化性能的影响，本文以35 kV电缆附件增强绝缘用硅橡胶为研究对象，利用过氧化物、硅氢加成两种硫化体系分别制作硫化硅橡胶试样并开展热老化试验，对比分析其力学性能和电气性能的变化特征。在热老化前期，两种硫化体系下硅橡胶均发生分子侧链的氧化交联反应和分子链间的再交联反应，交联度增大；热老化后期，交联体系结构和分子链被破坏，交联度变小。研究与测试结果表明：随着热老化时间的增加，硅橡胶试样拉伸强度和断裂伸长率逐渐减小，电导率先减小后增大、随温度升高而增大，相对介电常数逐渐增大、随温度升高而减小，介质损耗角正切逐渐增大、随温度升高而增大，击穿场强呈现先增后降趋势。硅氢加成硫化体系下的硅橡胶一直保持高交联度，在热老化后具备更优的力学性能和电气性能，而过氧化物硫化体系下的硅橡胶在硫化过程中产生强酸性副产物，在热老化后产生强极性基团，致使硅橡胶的热老化性能劣化。
- 增强绝缘用硅橡胶 /
- 热老化 /
- 过氧化物硫化 /
- 硅氢加成硫化 /
- 断裂伸长率 /
- 介电常数
Abstract: In order to explore the effects of different vulcanization systems on the thermal aging properties of sili-cone rubber used for enhanced insulation of cable accessories, silicone rubber was used for enhanced insulation of 35 kV cable accessories as the research object, and peroxide and hydrosilane addition vulcanization systems were used to produce vulcanized silicone rubber samples and carry out thermal aging tests to compare and analyze the mechanical and electrical properties of the rubber. In the early stage of thermal aging, the oxidative cross-linking reaction of molecular side chains and the re-cross-linking reaction between molecular chains occurred in both sili-cone rubber vulcanization systems, and the cross-linking degree increased. In the later stage of thermal aging, the cross-linking system structure and molecular chain were destroyed, and the cross-linking degree decreased. The research and test results show that the tensile strength and elongation at break of silicone rubber samples gradually decrease with the increase of thermal aging time, the conductivity decreases first and then increases with the increase of temperature, the relative dielectric constant increases gradually and decreases with the increase of temperature, the tangent of dielectric loss angle increases gradually and increases with the increase of temperature, and the breakdown field strength increases first and then decreases. The silicone rubber under the hydrosilane addition vulcanization system has always maintained high crosslinking degree and has better mechanical and electrical properties after thermal aging, while the silicone rubber under the peroxide vulcanization system produces strong acidic by-products during vulcanization and produces strong polar groups after thermal aging, resulting in the deterioration of the thermal aging performance of the silicone rubber.
- silicone rubber for reinforced insulation /
- thermal aging /
- peroxide vulcanization /
- hydrosilane addition vulcanization /
- elongation at break /
- dielectric constant

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图 1 甲基乙烯基硅橡胶结构式

Figure 1. Structure formula of methyl vinyl silicone rubber

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图 2 标准II型哑铃片示意图

Figure 2. Schematic diagram of standard type II dumbbell plate

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图 3 不同热老化时间硅橡胶试样的力学性能

Figure 3. Mechanical properties of silicone rubber samples with different thermal aging time

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图 4 不同热老化时间硅橡胶试样的FTIR图谱

Figure 4. FTIR spectra of silicone rubber samples with different thermal aging time

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图 5 不同热老化时间硅橡胶试样的电导率分布

Figure 5. Conductivity distribution of silicone rubber samples at different thermal aging time

γ_v—Conductivity; T—Temperature

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图 6 不同热老化时间硅橡胶试样的相对介电常数分布

Figure 6. Relative dielectric constant distribution of silicone rubber samples at different thermal aging time

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图 7 不同热老化时间硅橡胶试样的介质损耗角正切分布

Figure 7. Dielectric loss angle tangent distribution of silicone rubber samples with different thermal aging time

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图 8 不同热老化时间硅橡胶试样的击穿场强威布尔分布

Figure 8. Weibull distribution of breakdown field strength of silicone rubber samples at different thermal aging time

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图 9 不同热老化时间硅橡胶的击穿场强分布

Figure 9. Breakdown field strength distribution of silicone rubber at different thermal aging time

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图 10 硅橡胶硫化原理

Figure 10. Vulcanization principle of silicone rubber

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表 1 各试样的主要成分及质量分数

Table 1. Main components and mass fraction of each sample

Material	Mass fraction/wt%
Material	DCBP	PMHS
Silicone rubber	100	100
Silica	30	30
Structured control agents	5	5
2,4-dichlorobenzoyl peroxide (DCBP)	1.2	0
Platinum catalyst	0	0.7
Polymethyl hydro siloxane (PMHS)	0	0.6

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表 2 不同热老化时间硅橡胶试样的热延伸性能

Table 2. Thermal elongation properties of silicone rubber samples at different thermal aging time

Vulcanization system	Thermal aging time/ h	Thermal elongation/ %	Permanent deformation rate/%
DCBP vulcanized silicone rubber	0	83.0	4.0
	168	31.0	0.5
	336	16.5	1.5
	504	21.0	1.0
	672	28.0	1.0
PMHS vulcanized silicone rubber	0	18.5	1.0
	168	15.0	0.5
	336	16.0	0.0
	504	17.5	0.5
	672	19.0	0.5

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表 3 硅橡胶试样的各官能团指数

Table 3. Functional group index of each functional group of silicone rubber samples

Vulcanization system	Thermal aging time/h	Functional group index
Vulcanization system	Thermal aging time/h	Si—(CH₃)₂	Si—O—Si	Si—CH₃	C—H
DCBP vulcanized silicone rubber	0	8.35	3.29	0.48	1.90
	168	8.85	4.59	0.49	2.26
	336	8.89	4.44	0.50	2.21
	504	8.63	4.69	0.47	1.82
	672	8.80	3.76	0.47	1.87
PMHS vulcanized silicone rubber	0	7.33	6.23	0.47	1.99
	168	8.02	5.52	0.50	2.04
	336	8.65	6.71	0.62	3.22
	504	7.52	6.42	0.61	2.34
	672	6.91	6.43	0.49	1.97

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