β成核剂含量对等规聚丙烯电导电流和空间电荷特性的影响
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摘要
成核剂广泛用于调控聚丙烯的相变行为。为研究β成核剂含量对等规聚丙烯(iPP)电导电流和空间电荷特性的影响,制备了不同取代芳基杂环磷酸盐β成核剂(TMB-5)含量的iPP试样,开展了电导电流和温度场下空间电荷试验。结果表明,随着β成核剂的增加,β晶含量先增大后减小,而电导电流先减小后增大;25℃、-100 MV/m条件下极化30 min,六组iPP试样的电场畸变率均不超过6%;70℃、-100 MV/m条件下极化30 min,各组试样靠近阴极处均积聚正电荷,纯iPP试样电场畸变率最大(36.1%),而iPP-β0.1%(0.1%含量β成核剂)仅为13.2%。结合偏光显微观测和微晶团簇尺寸统计结果,从β成核剂的分散和成核过程分析了iPP试样中β晶含量变化的原因;利用极化和去极化过程中空间电荷的测试结果,并依据材料的微观结构与内部陷阱的相关性,解释了β成核剂含量对iPP试样内部空间电荷迁移和分布的影响过程。
β-nucleating agents(NAs) are widely used to regulate the phase transition behavior of polypropylene. To study the influence of β-NA content on conduction current and space charge characteristics in isotactic polypropylene(iPP), iPP samples filled with different mass fractions of substituted aromatic heterocyclic phosphate β-NAs(TMB-5) were prepared. Experiments of conduction current, dielectric, and space charge under temperature fields were carried out. The results show that β-crystal content increases firstly and then decreases with the increase of β-NA content, while conduction current is opposite. Moreover, electric field distortion ratio of six groups of iPP samples are no larger than 6% under-100 MV/m at 25℃ for 30 min of polarization. On the other hand, positive charge accumulates near the cathode in all groups under-100 MV/m at 70℃ for 30 min of polarization, and electric field distortion ratio of pure iPP samples is the largest(36.7%), while that of iPP-β 0.1%(containing 0.1% β-NAs) is only 13.9%. Combining polarized optical microscopy observations with statistics of the average size of crystallite clusters, cause for the changes of β-crystal content was analyzed from the dispersion and nucleation processes of β-NAs. Utilizing measurement results of space charge during polarization and depolarization processes, influence of β-NA content on the charge transit and distribution processes was explained based on the correlation between the microstructure and internal traps of materials.
β-nucleating agents(NAs) are widely used to regulate the phase transition behavior of polypropylene. To study the influence of β-NA content on conduction current and space charge characteristics in isotactic polypropylene(iPP), iPP samples filled with different mass fractions of substituted aromatic heterocyclic phosphate β-NAs(TMB-5) were prepared. Experiments of conduction current, dielectric, and space charge under temperature fields were carried out. The results show that β-crystal content increases firstly and then decreases with the increase of β-NA content, while conduction current is opposite. Moreover, electric field distortion ratio of six groups of iPP samples are no larger than 6% under-100 MV/m at 25℃ for 30 min of polarization. On the other hand, positive charge accumulates near the cathode in all groups under-100 MV/m at 70℃ for 30 min of polarization, and electric field distortion ratio of pure iPP samples is the largest(36.7%), while that of iPP-β 0.1%(containing 0.1% β-NAs) is only 13.9%. Combining polarized optical microscopy observations with statistics of the average size of crystallite clusters, cause for the changes of β-crystal content was analyzed from the dispersion and nucleation processes of β-NAs. Utilizing measurement results of space charge during polarization and depolarization processes, influence of β-NA content on the charge transit and distribution processes was explained based on the correlation between the microstructure and internal traps of materials.
引文
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[27]刘通,傅明利,侯帅,等.温度梯度影响高压直流电缆用交联聚乙烯中空间电荷分布的作用机理[J].高电压技术,2015,41(8):2665-2673.Liu Tong,Fu Mingli,Hou Shuai,et al.Mechanism of space charge distribution in XLPE used in HVDCcables under temerature gradient[J].High Voltage Engineering,2015,41(8):2665-2673.
[2]周远翔,赵健康,刘睿,等.高压/超高压电力电缆关键技术分析及展望[J].高电压技术,2014,40(9):2593-2612.Zhou Yuanxiang,Zhao Jiankang,Liu Rui,et al.Key technical analysis and prospect of high voltage and extra-high volt-age power cable[J].High Voltage Engineering,2014,40(9):2593-2612.
[3]何金良,党斌,周垚,等.挤压型高压直流电缆研究进展及关键技术述评[J].高电压技术,2015,41(5):1417-1429.He Jinliang,Dang Bin,Zhou Yao,et al.Reviews on research progress and key technology in extruded cables for HVDC transmission[J].High Voltage Engineering,2015,41(5):1417-1429.
[4]杜伯学,韩晨磊,李进,等.高压直流电缆聚乙烯绝缘材料研究现状[J].电工技术学报,2019,34(1):179-191.Du Boxue,Han Chenlei,Li Jin,et al.Research status of polyethylene insulation for high voltage direct current cables[J].Transactions of China Electrotechnical Society,2019,34(1):179-191.
[5]Tanaka Y,Takada T,Shinoda C,et al.Temperature dependence of space charge distribution in XLPEcable[C]//Annual Report Conference on Electrical Insulation and Dielectric Phenomena,Arlington,1994:334-339.
[6]郝建,伏进,侯兴哲,等.基于改进电声脉冲测试系统的油纸绝缘混合体系空间电荷动态行为特性[J].电工技术学报,2016,31(10):34-41.Hao Jian,Fu Jin,Hou Xingzhe,et al.Space charge migration characteristics of transformer oil-paper insulation based on the improved pulsed electroacoustic measurement system[J].Transactions of China Electrotechnical Society,2016,31(10):34-41.
[7]张冶文,赵晖,李宗泽,等.聚乙烯与聚丙烯中空间电荷注入特性的比较[J].高电压技术,2014,40(9):2613-2618.Zhang Yewen,Zhao Hui,Li Zongze,et al.Comparison of space charge injection behaviors between polythene and poly-propylene[J].High Voltage Engineering,2014,40(9):2613-2618.
[8]Kurahashi K,Matsuda Y,Ueda A,et al.Application of a novel polypropylene to the insulation of an electric power cable[J].Electrical Engineering in Japan,2006,155(3):1-8.
[9]Krentz T,Khani M M,Bell M,et al.Morphologically dependent alternating-current and direct-current breakdown strength in silica-polypropylene nanocomposites[J].Journal of Applied Polymer Science,2017,134(1):44347.
[10]张灵,周远翔,滕陈源,等.温度场下非等温结晶对低密度聚乙烯空间电荷特性的影响[J].高电压技术,2017,43(2):420-428.Zhang Ling,Zhou Yuanxiang,Teng Chenyuan,et al.In-fluence of non-isothermal crystallization on space charge characteristics in low-density polyethylene at temperature fields[J].High Voltage Engineering,2017,43(2):420-428.
[11]廖瑞金,柳海滨,柏舸,等.纳米SiO2/芳纶绝缘纸复合材料的空间电荷特性和介电性能[J].电工技术学报,2016,31(12):40-48.Liao Ruijin,Liu Haibin,Bai Ge,et al.Space charge characteristics and dielectric properties of nanoSiO2/aramid paper composite[J].Transactions of China Electrotechnical society,2016,31(12):40-48.
[12]Dong Mu,Guo Zhaoxia,Su Zhiqiang,et al.The effects of crystallization condition on the microstructure and thermal stability of istactic polypropylene nucleated byβ-form nucleating agent[J].Journal of Applied Polymer Science,2011,119(3):1374-1382.
[13]Wu Yunhui,Zha Junwei,Li Weikang,et al.Aremarkable suppression on space charge in isotatic polypropylene by inducing theβ-crystal formation[J].Applied Physics Letters,2015,115(11):1129011-1129015.
[14]Zhang Ling,Zhang Yunxiao,Zhou Yuanxiang,et al.Crystalline modification and its effects on dielectric breakdown strength and space charge behavior in isotactic polypropylene[J].Polymers,2018,10(4):406.
[15]Zhou Yuanxiang,Wang Ninghua,Yan Pin,et al.Annealing effect on DC conduction in polyethylene films[J].Journal of Electrostatics,2003,57(3-4):381-388.
[16]Jones A T,Aizlewood J M,Beckett D R.Crystalline forms of isotactic polypropylene[J].Macromolecular Chemistry&Physics,1964,75(1):134-158.
[17]雷清泉,石林爽,田付强,等.电晕老化前后100HN和100CR聚酰亚胺薄膜的电导电流特性实验研究[J].中国电机工程学报,2010,30(13):109-114.Lei Qingquan,Shi Linshuang,Tian Fuqiang,et al.Experi-mental research on conduction current characteristics of 100HN and 100CR polyimide film before and after corona aging[J].Proceedings of the CSEE,2010,30(13):109-114.
[18]陈季丹.电介质物理学[M].北京:机械工业出版社,1982:227-228.
[19]Mohmeyer N,Schmidt H W,Kristiansen P M,et al.In-fluence of chemical structure and solubility of bisamide additives on the nucleation of isotactic polypropylene and the improvement of its charge storage properties[J].Macromolecules,2006,39(17):5760-5767.
[20]Nagasawa S,Fujimori A,Masuko T,et al.Crystallization of polypropylene containing nucleators[J].Polymer,2005,46(14):5241-5250.
[21]Zhang Guangping,Xin Zhong,Yu Jianyong,et al.Nucleating efficiency of organic phosphates in polypropylene[J].Journal of Macromolecular Science Part B,2003,42(3-4):467-478.
[22]Dong Mu,Guo Zhaoxia,Yu Jian,et al.Study of the assembled morphology of aryl amide derivative and its influence on the nonisothermal crystallization of isotactic polypropylene[J].Journal of Polymer Science Part B:Polymer Physics,2009,47:314-325.
[23]Mazzanti G,Montanari G C,Palmieri F,et al.Apparent trap-controlled mobility evaluation in insulating polymers through depolarization characteristics derived by space charge measurements[J].Journal of Applied Physics,2003,94(9):5997-6004.
[24]Zhang Ling,Khani M M,Krentz T M,et al.Suppression of space charge in crosslinked polyethylene filled with poly(stearyl methacrylate)-grafted SiO2 nanoparticles[J].Applied Physics Letters,2017,110(13):132903.
[25]吴建东.低密度聚乙烯纳米复合介质中电荷输运的实验研究和数值模拟[D].上海:上海交通大学,2012.
[26]Montanari G C,Mazzanti G,Palmieri F,et al.Mobility evaluation from space charge measurements performed by the pulsed electroacoustic technique[C]∥Proceedings of the 6th International Conference on Properties and Applications of Dielectric Materials,Xi’an,2000:38-41.
[27]刘通,傅明利,侯帅,等.温度梯度影响高压直流电缆用交联聚乙烯中空间电荷分布的作用机理[J].高电压技术,2015,41(8):2665-2673.Liu Tong,Fu Mingli,Hou Shuai,et al.Mechanism of space charge distribution in XLPE used in HVDCcables under temerature gradient[J].High Voltage Engineering,2015,41(8):2665-2673.