基于分子模拟的硅烷偶联剂改性氮化硼掺杂芳纶复合材料热力学性能研究

doi:10.19595/j.cnki.1000-6753.tces.240780

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摘要

为探究不同硅烷偶联剂改性的氮化硼填料对芳纶复合体系热力学性能的影响规律,该文选取KH550、KH560、KH580和QX1324共4种硅烷偶联剂对氮化硼（BN）进行接枝改性,在Materials Studio中构建了改性氮化硼掺杂对位芳纶（PPTA）的复合模型,并基于分子动力学方法探究了复合模型的热导率、玻璃化转变温度、力学性能以及分子间作用力等性质。结果表明,偶联剂改性能够进一步提高复合体系的热力学稳定性。其中,BN-QX1324/PPTA体系的改性效果最佳,其热导率为0.206 W/(m·K),较改性前提高74.16%,玻璃化转变温度达到597.746 K,杨氏模量相比改性前增强13.43%。BN-KH550/PPTA、BN-KH560/PPTA和BN-KH580/PPTA体系的玻璃化转变温度分别为562.192 K、568.581 K和547.264 K,杨氏模量依次提升8.09%、10.80%和7.21%。借助径向分布函数、内聚能密度、自由体积分数、氢键等参数计算从分子热运动和分子间相互作用力层面阐明了复合体系热力学性能提升的根本原因,最后通过实验验证了仿真结果的有效性。该文可为基于分子模拟手段进行偶联剂改性筛选和高性能对位芳纶复合体系的设计提供一定的理论指导。

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关键词 ：对位芳纶, 氮化硼, 硅烷偶联剂, 分子模拟, 热力学性能

Abstract：

PPTA is a high-insulation, high-modulus fiber material that is widely utilized in the insulation protection of power equipment. However, its inherently low thermal conductivity limits the ability to dissipate heat effectively. Recently, nano-doping modification and coupling agent grafting have emerged as effective methods for enhancing the thermal properties of high polymers. BN is an inorganic filler with favorable thermodynamic properties while there is limited research on BN modified with coupling agents doped PPTA. To investigate the impact of BN fillers modified with different silane coupling agents on the thermomechanical properties of aramid composites, four types of silane coupling agents (KH550, KH560, KH580, and QX1324) were selected, various modified BN composite models were created by doping para-aramid (PPTA) using Materials Studio. The thermal conductivity, glass transition temperature, mechanical properties, and intermolecular interactions of the composite models were analyzed by the molecular dynamics method.
Firstly, the thermal conductivity of the composite system was calculated using the rNEMD method. The thermal conductivity of the composite systems modified with coupling agents were significantly enhanced. Specifically, the thermal conductivity of BN-KH560/PPTA and BN-QX1324/PPTA increased by 82.49% and 74.16%, respectively, compared with pure PPTA. RDF analysis indicated that the interaction between the end group of KH560 and QX1324 coupling agents and PPTA was more pronounced. Additionally, the glass transition temperature of the composite system was analyzed by the specific volume-temperature method, the BN-QX1324/PPTA system reached 597.746 K, which represented a 12.93% increase.
Regarding mechanical properties, the Young's modulus and shear modulus of the composite systems were consistently higher than those of pure PPTA over the temperature range from 300 K to 700 K. At 300 K, the Young's modulus of the BN/PPTA, BN-KH550/PPTA, BN-KH560/PPTA, BN-KH580/PPTA, and BN-QX1324/PPTA systems was, on average, 9.95% higher compared to PPTA. Furthermore, the BN-QX1324/PPTA system demonstrated greater resistance to the degradation of mechanical properties at high temperature.
Regarding structural parameters, the reasons for the improved performance of the composite systems were elucidated through calculations of cohesive energy density, free volume fraction, hydrogen bond number, and other parameters that assessed intermolecular interactions. Modified BN enhanced the cohesive energy density of the systems through hydrogen bonding and van der Waals force, further strengthening the interaction within the composite systems. Notably, due to the strong electronegativity of fluorine groups, the cohesive energy density of the BN-QX1324/PPTA system increased the most, with an average rise of 13.32%. Additionally, it exhibited strong resistance to external electric field interference.
To verify the validity of the calculation results, the BN-QX1324/PPTA system, which showed the best modification effects in the simulation, was selected for experimental investigation. The results indicated that the thermal conductivity, glass transition temperature, Young's modulus, and breakdown field strength of the PPTA/BN-F system were significantly improved that compared to the pre-modification values, and the trends were consistent with the simulation results. This study validates the reliability of the simulation calculations and show that the enhanced intermolecular interactions between the fluorinated group and PPTA in the QX1324 coupling agent are the underlying reasons for the observed performance improvements.

Key words： Para-aramid boron nitride silane coupling agent molecular simulation thermodynamic property

收稿日期: 2024-05-14

PACS:

TM215.6

基金资助:

中央高校基本科研业务费专项资金资助项目（2023MS107）

通讯作者: 刘博闻女,1990年生,讲师,研究方向为先进电工材料与电力设备故障诊断等。E-mail：lbw357@ncepu.edu.cn

作者简介: 黄岩城男,1999年生,硕士研究生,研究方向新型电工绝缘材料与电气设备在线监测。E-mail：756309729@qq.com

引用本文:

黄岩城, 刘博闻, 董合, 耿江海, 律方成. 基于分子模拟的硅烷偶联剂改性氮化硼掺杂芳纶复合材料热力学性能研究[J]. 电工技术学报, 0, (): 2492944-2492944. Huang Yancheng, Liu Bowen, Dong He, Geng Jianghai, Lü Fangcheng. Thermomechanical Properties of Silane Coupling Agents Modified Boron Nitride Doped Aramid Composites Based on Molecular Simulation. Transactions of China Electrotechnical Society, 0, (): 2492944-2492944.

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