Abstract:In the oil-immersed transformer, the cellulose insulating paper is prone to partial discharge, which makes the insulating paper easy to break down and causes security risks. Therefore, it is important to improve the insulation performance of insulating paper. At present, the primary method is to add inorganic nanoparticles to insulating paper. By doping nanoparticles with a high specific surface area and surface energy in insulating paper, charge carriers can be adsorbed to reduce the energy and thus improve the insulation characteristics of insulating paper. However, the nanoparticle is easy to agglomerate, accumulating charge carriers in the nanoparticle aggregation area, resulting in partial discharge and breakdown. The silane coupling agent is often used to improve the agglomeration of nanoparticles. One end of the silane coupling agent can be combined with the hydroxyl group (-OH) on the surface of nanoparticles through a condensation reaction. The other end of the amino group can be combined with the hydroxyl group on the surface of insulating paper through hydrogen bonding force. Thus, the dispersion of nanoparticles on the surface of insulating paper is improved. However, the hydroxyl content on the surface of inorganic nanoparticles is low. The effect of direct modification with a silane coupling agent could be better, and the activity of the silane coupling agent will decrease with time. If the number of hydroxyls on the surface of nanoparticles can be increased, the effect of the silane coupling agent can be improved. Plasma grafting can graft corresponding functional groups on the surface of materials according to the application requirements, widely used in material surface modification. This paper uses high-frequency AC power to drive the dielectric barrier discharge (DBD) reactor to generate plasma in the humid nitrogen and oxygen mixture. The influence of the surface modification method of nano-SiO2 particles on the dispersion of nano-SiO2 particles and the insulation characteristics of insulating paper is studied. By grafting hydroxyl free radicals (·OH) from water molecule ionization onto the surface of nano-SiO2 particles, nano-SiO2 particles could be modified by hydroxylation, and more silane coupling agents could be grafted to improve the agglomeration. Accordingly, the cellulose insulating paper doped with nano-SiO2 particles was prepared by the in-situ polymerization method. The chemical composition, morphology, functional groups, and the number of grafted hydroxyl groups on the surface of nano-SiO2 particles before and after plasma modification were characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FTIR), and specific surface and porosity analyzer (BET) combined with titration. The effects of plasma treatment conditions and modification steps on the breakdown field and volume resistivity were investigated. The results show that the content of oxygen (O) element and the hydroxyl absorption peak on the surface of nano-SiO2 particles are significantly enhanced after plasma treatment, and the number of hydroxyl on the surface of nano-SiO2 particles reaches the highest when the plasma modification time is 5 min and the air relative humidity is 75%. SEM observation shows that the dispersion of nano-SiO2 particles in insulating paper is improved after plasma hydroxylation modification. When the relative humidity of air is 75% and the mass fraction of nano-SiO2 particles is 3%, the DC breakdown field and volume resistivity of insulating paper reach the maximum. The best modification procedure is to treat nano-SiO2 particles with plasma modification and silane coupling agent to obtain the optimal breakdown field strength and volume resistivity of insulating paper. It is confirmed that plasma hydroxylation-modified nano-SiO2 particles can improve their dispersion on the surface of insulating paper and improve the limiting effect on charge carriers.
[1] Ali M, Eley C, Emsley A M, et al.Measuring and understanding the ageing of KRAFT insulating paper in power transformers[J]. IEEE Electrical Insulation Magazine, 1996, 12(3): 28-34. [2] 廖瑞金, 巩晶, 桑福敏, 等. 利用TGA及DSC研究变压器油浸绝缘纸的老化[J]. 高电压技术, 2010, 36(3): 572-577. Liao Ruijin, Gong Jing, Sang Fumin, et al.Experimental study on the ageing of transformer oil-immersed paper using TGA and DSC[J]. High Voltage Engineering, 2010, 36(3): 572-577. [3] Frimpong G K, Oommen T V, Asano R.A survey of aging characteristics of cellulose insulation in natural ester and mineral oil[J]. IEEE Electrical Insulation Magazine, 2011, 27(5): 36-48. [4] Zhang Yiyi, Li Yi, Zheng Hanbo, et al.Microscopic reaction mechanism of the production of methanol during the thermal aging of cellulosic insulating paper[J]. Cellulose, 2020, 27(5): 2455-2467. [5] Wu Shilin, Zhang Cheng, Zhang Chuansheng, et al.Nano-sized composite improving the insulating perfor- mance of insulating paper using low temperature plasmas[J]. Nanotechnology, 2021, 32(18): 185704. [6] Liao Ruijin, Lü Cheng, Yang Lijun, et al.The insulation properties of oil-impregnated insulation paper reinforced with nano-TiO2[J]. Journal of Nanomaterials, 2013, 2013(1): 1. [7] Zhang Cheng, Ma Yiyang, Kong Fei, et al.Atmo- spheric pressure plasmas and direct fluorination treatment of Al2O3-filled epoxy resin: a comparison of surface charge dissipation[J]. Surface and Coatings Technology, 2019, 362: 1-11. [8] Li Shengtao, Yu Shihu, Feng Yang.Progress in and prospects for electrical insulating materials[J]. High Voltage, 2016, 1(3): 122-129. [9] Tanaka T, Montanari G C, Mulhaupt R.Polymer nano-composites as dielectrics and electrical insulation- perspectives for processing technologies, material characterization and future applications[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2004, 11(5): 763-784. [10] 张冬海, 张晖, 张忠, 等. 纳米技术在高性能电力复合绝缘材料中的工程应用[J]. 中国科学: 化学, 2013, 43(6): 725-743. Zhang Donghai, Zhang Hui, Zhang Zhong, et al.Industry applications of nanotechnology in high performance insulation composites[J]. Scientia Sinica Chimica, 2013, 43(6): 725-743. [11] 王小波. 硅烷偶联剂修饰纳米SiO2对其改性纤维素绝缘纸性能的微观机理研究[D]. 重庆: 西南大学, 2019. [12] Yan Shuiqiang, Liao Ruijin, Yang Lijun, et al.Influence of nano-Al2O3 on electrical properties of insulation paper under thermal aging[C]//IEEE International Conference on High Voltage Engin- eering and Application, Chengdu, China, 2016: 1-4. [13] 刘娟. 等离子体改性Al2O3纳米粒子对PI复合薄膜介电特性影响研究[D]. 成都: 西南交通大学, 2020. [14] 杨国清, 冯媛媛, 王德意, 等. 等离子体表面改性玻璃纤维增强的环氧树脂性能研究[J]. 大电机技术, 2017(6): 10-15. Yang Guoqing, Feng Yuanyuan, Wang Deyi, et al.Study on mechnical properties of epoxy resin reinforced by glass fiber modified by plasmas surface[J]. Large Electric Machine and Hydraulic Turbine, 2017(6): 10-15. [15] 吴旭辉, 吴广宁, 杨雁, 等. 等离子体改性纳米粒子对聚酰亚胺复合薄膜陷阱特性影响[J]. 中国电机工程学报, 2018, 38(11): 3410-3418. Wu Xuhui, Wu Guangning, Yang Yan, et al.Influence of nanoparticles plasma-modification on trap pro- peties of polyimide composite films[J]. Proceedings of the CSEE, 2018, 38(11): 3410-3418. [16] Scaffaro R. Maio A.Enhancing the mechanical performance of polymer based nanocomposites by plasma-modification of nanoparticles[J]. Polymer Testing, 2012, 31(7): 889-894. [17] 罗凡. 低温等离子体改性碳材料吸附性能的研究[D]. 杭州: 浙江大学, 2009. [18] 王宏, 李来风, 张浩, 等. 多壁碳纳米管表面等离子体有机聚合改性[J]. 复合材料学报, 2007, 24(3): 121-125. Wang Hong, Li Laifeng, Zhang Hao, et al.Surface modification of carbon nanotubes by plasma polymerization[J]. Acta Materiae Compositae Sinica, 2007, 24(3): 121-125. [19] Shi Donglu, Wang Shixing, van Ooij W J, et al. Uniform deposition of ultrathin polymer films on the surfaces of Al2O3 nanoparticles by a plasma treat- ment[J]. Applied Physics Letters, 2001, 78(9): 1243-1245. [20] 刘洪, 薛屺, 代维. 表面改性处理对氧化铝/酚醛树脂粘接强度的影响[J]. 热固性树脂, 2013, 28(3): 33-35. Liu Hong, Xue Qi, Dai Wei.Effect of surface modification on the bonding strength of Al2O3/ phenolic resin[J]. Thermosetting Resin, 2013, 28(3): 33-35. [21] 胡婷, 柳欢欢, 周竹君, 等. 纳米SiO2复合改性绝缘纸的制备[J]. 绝缘材料, 2017, 50(6): 22-26. Hu Ting, Liu Huanhuan, Zhou Zhujun, et al.Prepar- ation of nano-SiO2 composite modified insulation paper[J]. Insulating Materials, 2017, 50(6): 22-26. [22] 陈杰, 朱力. 纳米SiO2改性绝缘纸的机械老化与电老化性能研究[J]. 合成材料老化与应用, 2020, 49(6): 52-54. Chen Jie, Zhu Li.Study on the mechanical and electrical aging properties of nano-SiO2 modified insulating paper[J]. Synthetic Materials Aging and Application, 2020, 49(6): 52-54. [23] 欧阳兆辉, 伍林, 李孔标, 等. 气相法改性纳米二氧化硅表面[J]. 化工进展, 2005, 24(11): 1265-1268. Ouyang Zhaohui, Wu Lin, Li Kongbiao, et al.Surface modification of nano silicon dioxide by gas phase method[J]. Chemical Industry and Engineering Progress, 2005, 24(11): 1265-1268. [24] 刘云鹏, 郁利超, 刘贺晨, 等. 冲击电压下160kV高压直流电缆绝缘材料击穿特性研究[J]. 绝缘材料, 2017, 50(7): 49-54. Liu Yunpeng, Yu Lichao, Liu Hechen, et al.Study on breakdown characteristic of 160kV HVDC insulating materials under impulse voltage[J]. Insulating Materials, 2017, 50(7): 49-54. [25] Yan Wei, Phung B T, Han Zhaojun, et al.Plasma polymer-coated on nanoparticles to improve dielectric and electrical insulation properties of nanocom- posites[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2014, 21(2): 548-555. [26] 刘阳. 低气压低温等离子体改性纳米SiO2/环氧树脂绝缘特性研究[D]. 西安: 西安理工大学, 2020. [27] 杨越. 等离子体改性微米氧化铝掺杂树脂的绝缘及力学性能研究[D]. 西安: 西安理工大学, 2017. [28] Musa F, Bashir N, Ahmad M, et al.Investigating the influence of plasma-treated SiO2 nanofillers on the electrical treeing performance of silicone-rubber[J]. Applied Sciences, 2016, 6(11): 348. [29] 陈向荣, 王启隆, 黄小凡, 等. 硅烷偶联剂改性纳米AlN对碳化硅器件封装用有机硅弹体耐电及老化特性的影响[J]. 电工技术学报, 2022, 37(16): 4235-4249. Chen Xiangrong, Wang Qilong, Huang Xiaofan, et al.Effect of silane coupling agent modified nano-AlN on electrical and aging properties of silicone elastomer for SiC device packaging[J]. Transactions of China Electrotechnical Society, 2022, 37(16): 4235-4249. [30] 莫洋, 杨丽君, 鄢水强, 等. 掺杂纳米Al2O3对纤维素绝缘纸电寿命的影响及机理[J]. 电工技术学报, 2018, 33(19): 4618-4626. Mo Yang, Yang Lijun, Yan Shuiqiang, et al.Influence and mechanism of doped nano-Al2O3 on electrical life of cellulose insulating paper[J]. Transactions of China Electrotechnical Society, 2018, 33(19): 4618-4626.