College of Computer Science and Technology, Heilongjiang Institute of Technology, Harbin 150050, China.
Key Laboratory of Cold Region Urban and Rural Human Settlement Environment Science and Technology, Ministry of Industry and Information Technology, School of Architecture, Harbin Institute of Technology, Harbin 150006, China.
Int J Mol Sci. 2022 Aug 21;23(16):9450. doi: 10.3390/ijms23169450.
In order to restrain electric-stress impacts of water micro-droplets in insulation defects under alternating current (AC) electric fields in crosslinked polyethylene (XLPE) material, the present study represents chemical graft modifications of introducing chloroacetic acid allyl ester (CAAE) and maleic anhydride (MAH) individually as two specific polar-group molecules into XLPE material with peroxide melting approach. The accelerated water-tree aging experiments are implemented by means of a water-blade electrode to measure the improved water resistance and the affording mechanism of the graft-modified XLPE material in reference to benchmark XLPE. Melting−crystallization process, dynamic viscoelasticity and stress-strain characteristics are tested utilizing differential scanning calorimeter (DSC), dynamic thermomechanical analyzer (DMA) and electronic tension machine, respectively. Water-tree morphology is observed for various aging times to evaluate dimension characteristics in water-tree developing processes. Monte Carlo molecular simulations are performed to calculate free-energy, thermodynamic phase diagram, interaction parameter and mixing energy of binary mixing systems consisting of CAAE or MAH and water molecules to evaluate their thermodynamic miscibility. Water-tree experiments indicate that water-tree resistance to XLPE can be significantly improved by grafting CAAE or MAH, as indicated by reducing the characteristic length of water-trees from 120 to 80 μm. Heterogeneous nucleation centers of polyethylene crystallization are rendered by the grafted polar-group molecules to ameliorate crystalline microstructures, as manifested by crystallinity increment from 33.5 to 36.2, which favors improving water-tree resistance and mechanical performances. The highly hydrophilic nature of CAAE can evidently inhibit water molecules from aggregating into water micro-droplets in amorphous regions between crystal lamellae, thus acquiring a significant promotion in water-tree resistance of CAAE-modified XLPE. In contrast, the grafted MAH molecules can enhance van der Waals forces between polyethylene molecular chains in amorphous regions much greater than the grafted CAAE and simultaneously act as more efficient crystallization nucleation centers to ameliorate crystalline microstructures of XLPE, resulting in a greater improvement (relaxation peak magnitude increases by >10%) of mechanical toughness in amorphous phase, which primarily accounts for water-tree resistance promotion.
为了抑制交联聚乙烯(XLPE)材料中交流电场下绝缘缺陷中水微滴的电场应力影响,本研究采用过氧化物熔融法,分别将氯乙酸烯丙酯(CAAE)和马来酸酐(MAH)这两种特定的极性基团分子作为两种特定的极性基团分子引入 XLPE 材料中进行化学接枝改性。通过水刀电极进行加速水树老化实验,以测量改进的耐水性和接枝改性 XLPE 材料相对于基准 XLPE 的提供机制。利用差示扫描量热仪(DSC)、动态热机械分析仪(DMA)和电子拉力机分别测试熔融-结晶过程、动态粘弹性和应力-应变特性。观察不同老化时间的水树形态,以评估水树发展过程中的尺寸特性。通过蒙特卡罗分子模拟计算由 CAAE 或 MAH 和水分子组成的二元混合系统的自由能、热力学相图、相互作用参数和混合能,以评估其热力学混溶性。水树实验表明,通过接枝 CAAE 或 MAH,XLPE 的水树阻力可以显著提高,特征长度从 120μm 降低到 80μm。接枝的极性基团分子为聚乙烯结晶提供了异质成核中心,改善了结晶微结构,结晶度从 33.5%增加到 36.2%,有利于提高水树阻力和机械性能。CAAE 的高亲水性可明显抑制无定形区中水分子聚集形成水微滴,从而显著提高 CAAE 改性 XLPE 的水树阻力。相比之下,接枝的 MAH 分子可以增强无定形区中聚乙烯分子链之间的范德华力,比接枝的 CAAE 大得多,同时作为更有效的结晶成核中心,改善 XLPE 的结晶微结构,导致无定形相的机械韧性(松弛峰幅度增加>10%)有较大提高,这主要是水树阻力提高的原因。