Effect of thermal aging on the physicochemical and dielectric properties of ethylene-propylene-diene monomer self-fusing insulation
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摘要: 本文研究了热老化对三元乙丙橡胶(EPDM)自熔式接头绝缘理化性能和介电性能的影响，分析了老化前后试样的分子结构、力学性能、微观结构及介电性能。结果表明：热老化后，EPDM绝缘的分子链发生氧化断裂反应，生成较多的含氧基团，使羰基指数增大。EPDM分子主链断裂造成的分子链柔顺性降低，及黏胶分子间的凝胶化过程，共同导致试样的储能模量和损耗模量升高，损耗因子降低。由于热老化破坏了试样的分子结构，使拉伸性能下降，但自熔式绝缘中的黏胶分子会与交联聚乙烯绝缘表面发生粘结，形成紧密的复合界面，使剥离强度提高。老化后的试样内部极性基团数量增多，转向极化增强，损耗增加。热老化过程中，分子间作用力对载流子的束缚力减弱和黏胶分子的溶胀作用，使载流子更容易跃迁参与导电，体积电导率增大；同时，EPDM分子结构的松散无序性，使电荷更容易迁移，自由电子数量增多，击穿场强降低。
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关键词:
- 三元乙丙橡胶自熔式绝缘 /
- 热老化 /
- 理化性能 /
- 介电性能 /
- 界面特性
Abstract: The effects of thermal aging on the physicochemical and dielectric properties of EPDM (ethylene-propylene-diene monomer) self-fusing insulation were investigated. The molecular structure, mechanical properties, microstructure, and dielectric performance of the samples before and after aging were analyzed. The results indicate the molecular chains of EPDM insulation are fractured by oxidation, resulting in the formation of a greater number of oxygen-containing groups and an increase in the carbonyl index after thermal aging. The rupture of the main molecular chains reduces the flexibility of EPDM and the gelation process among the adhesive molecules, which lead to the increase of the storage modulus and loss modulus, the decrease of the loss factor. The tensile property is decreased due to the molecular structure of the samples are destroyed during thermal aging, but the adhesive molecules in the self-fusing insulation will bond with the surface of the crosslinked polyethylene insulation to form a tight composite interface, which improves peel strength. The number of polar groups in the aged samples increase, orientation polarization is enhances and the losses increases. In the process of thermal aging, the weakening of intermolecular forces reduces the binding force on charge carriers, and the swelling effect of the adhesive molecules facilitates make it easier for charge carriers to transition and participate in conduction, resulting in an increased volumetric conductivity. Additionally, the loose disorder of the EPDM molecular structure allows for easier charge migration, increases the number of free electrons, and reduces the breakdown strength. -
图 1 三元乙丙橡胶(EPDM)自熔式绝缘材料老化前后的红外光谱图
Figure 1. FTIR spectra of ethylene-propylene-diene monomer (EPDM) self-fusing insulation before and after aging
图 3 EPDM老化前后的动态力学性能，(a) 储能模量，(b) 损耗模量，(c) 损耗因子
Figure 3. DMA spectrum of EPDM before and after aging,(a) energy storage modulus,(b) energy consumption modulus,(c) loss factor
图 5 XLPE/EPDM复合绝缘界面老化前(a)后(b)的偏光显微镜图
Figure 5. PLM images of the XLPE/EPDM composite insulation interface before (a) and after (b) aging
图 6 XLPE/EPDM复合绝缘界面老化前(a)后(b)的SEM图像
Figure 6. SEM images of XLPE/EPDM composite insulation interface before (a) and after (b) aging
图 7 不同温度下EPDM的相对介电常数(a)和介质损耗角正切(b)
Figure 7. Relative permittivity (a) and dielectric loss tangent (b) of EPDM at different temperatures
图 9 EPDM击穿场强的Weibull分布图
Figure 9. Weibull distribution diagram of breakdown field strength of EPDM
表 1 EPDM老化前后的红外光谱指数
Table 1. FTIR spectra index of EPDM before and after aging
Sample Methylene
index M1Methyl
index M2Carbonyl
index CBefore aging 0.96 1.58 1.35 After aging 0.74 1.53 2.38 
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表 2 XLPE/EPDM老化前后的剥离性能
Table 2. Peeling performance of XLPE/EPDM before and after aging
Sample Peeling force/N Peel strength/(N·cm−1) Before aging 16.9 8.5 After aging 29.8 -
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表 3 EPDM的活化能
Table 3. Activation energy of EPDM
Sample Activation energy/eV Before aging 0.77 After aging 0.75
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表 4 EPDM击穿场强的Weibull分布参数
Table 4. Weibull distribution parameters of breakdown field strength of EPDM
Sample E0/(kV·mm−1) β Before aging 30.02 11.92 After aging 27.35 11.27 Notes: E0 represents the breakdown strength of the sample at 63.2% failure probability; β represents the degree of dispersion of data.
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