空间电荷与直流电导联合测试技术用于纳米MgO抑制XLPE中空间电荷的研究

粒径70nm的MgO以不同浓度与交联聚乙烯(XLPE)共混制成聚合物纳米复合介质。采用自主研发的四电极系统同时测量复合介质的高场电导特性和空间电荷分布。通过强场电导实验发现,在室温下,XLPE及纳米MgO/XLPE复合介质的电导机理不是单纯的空间电荷限制电流(SCLC)。此外,添加纳米MgO可以明显地提高空间电荷的注入阈值,并且在低于空间电荷注入阈值的电场下,复合介质的电导电流密度随纳米MgO浓度的增加,先减小后增大。最后从空间电荷的实验数据验证了纳米MgO能有效抑制XLPE中空间电荷,并进一步定性地认为纳米Mgo的添加提高了电子注入的电场强度阈值。     

纳米MgO掺杂聚乙烯中空间电荷行为的研究

介绍了采用电声脉冲法测量纯低密度聚乙烯以及氧化镁／低密度聚乙烯（MgO／LDPE）纳米复合介质中的空间电荷,讨论了不同含量的MgO以及不同型号LDPE作为基础材料对复合介质内空间电荷分布的影响。实验结果表明：随着直流电场的增加,在纯聚乙烯中产生电荷注入现象,且随着加压时间的增加,注入的同极性电荷有向另一电极移动的趋势。少量的MgO可以有效抑制复合介质中的空间电荷注入,随着MgO含量的增加,对复合介质的空间电荷注入抑制效果逐渐减弱。     

基于空间电荷的纳米MgO/LDPE中电荷输运的计算方法研究

为定量分析研究纳米氧化镁(MgO)/低密度聚乙烯(LDPE)复合介质的空间电荷行为,将粒径20 nm的纳米MgO颗粒以不同浓度填充到LDPE,并对纳米复合介质的空间电荷分布进行了实验研究。通过空间电荷实验的结果,对其进行多种方法的计算分析,计算分析结果表明:1)浓度为0.5wt%和2wt%的积累空间电荷的平均体电荷密度最大,而浓度1wt%的纳米MgO/LDPE的平均体电荷密度最小;2)浓度为2wt%的纳米MgO/LDPE的视在迁移率和体电荷密度衰减速率最高,其次是浓度为0.5wt%的,最低的是浓度为1wt%的纳米复合介质;3)浓度为1wt%的纳米MgO/LDPE的陷阱深度最大,其次是浓度为0.5wt%的,而陷阱深度最小的是浓度为2wt%的纳米Mg O/LDPE;4)浓度为2wt%的纳米MgO/LDPE试样中的场强畸变最大,其次是浓度为1wt%的,而场强发生畸变幅度最小的是浓度为0.5wt%的纳米MgO/LDPE。     

不同表面处理剂对纳米MgO/LDPE空间电荷行为的影响

为研究不同表面处理剂对纳米MgO/低密度聚乙烯(LDPE)复合介质空间电荷行为的影响,将经过不同表面处理的纳米MgO颗粒以不同质量分数填充到低密度聚乙烯中,制得纳米复合介质,并对不同纳米复合介质的微观特性结构和空间电荷分布进行了实验研究。微观特性研究表明,经过表面处理,无机纳米颗粒与聚合物的结合作用得到增强,复合介质结晶度增加;空间电荷实验表明,添加经过不同表面处理的纳米MgO后复合介质在短路时阴极和阳极均积累了同极性电荷。此外,在不同无机纳米颗粒填充质量分数下,经过不同表面处理剂修饰后的纳米复合介质内部积累的空间电荷得到不同程度的抑制。总体而言,铝酸酯偶联剂对纳米MgO颗粒的表面处理效果相对较好。     

添加纳米MgO对交联聚乙烯中直流接地电树枝的影响

对交联聚乙烯(cross linked polyethylene, XLPE)材料与质量分数为05%的 MgO/XLPE纳米复合材料分别进行了直流接地电树枝实验与基于电声脉冲法的空间电荷测量。电树枝实验表明,正极性下MgO/XLPE纳米复合材料表现出更高的50%电树枝引发电压;空间电荷测量结果表明XLPE中有更多同极性电荷注入,说明纳米颗粒的添加阻碍了针尖处同极性电荷的注入与抽出,进而阻碍了电树枝引发。正极性下MgO/XLPE纳米复合材料表现出更小的平均电树枝长度与宽度,这是由于高场强区产生的载流子与纳米颗粒发生碰撞,导致电树枝生长较慢。此外,正极性下MgO/XLPE纳米复合材料中平均电树枝长宽比随电压升高下降更快,这是由于电树枝无法穿透纳米颗粒,只能从其表面绕过,导致了电树枝通道方向的改变与细小分枝的产生。     

MgO/LDPE纳米复合材料制备及其空间电荷特性

为了降低低密度聚乙烯中的空间电荷积累,在自制纳米MgO粉体的基础上,采用熔融共混法,制备了氧化镁/低密度聚乙烯(MgO/LDPE)纳米复合材料,并通过扫描电镜(SEM)观察了MgO/LDPE纳米复合材料中的MgO粒径大小和分散情况,采用差热扫描量热法(DSC)确定了不同MgO质量分数纳米复合材料的结晶度,采用电声脉冲法(PEA)测量了不同MgO质量分数纳米复合材料的空间电荷分布,测量了不同MgO质量分数纳米复合材料的拉伸性能。试验结果表明,MgO/LDPE纳米复合材料体系中,MgO粒径约为50nm,且分散均匀;不同MgO质量分数纳米复合材料的弹性模量和抗张强度均高于纯LDPE的,且MgO质量分数为2%时达到最大值;不同MgO质量分数纳米复合材料的结晶度均高于纯LDPE的;纳米MgO能抑制空间电荷的注入和其在材料体内的迁移,质量分数为3%时,MgO/LDPE纳米复合材料中的空间电荷得到了良好的抑制。     

半导电材料对纳米MgO/XLPE复合介质空间电荷影响的研究

聚合物纳米复合介质中空间电荷的注入与半导电电极材料密切相关,文中采用电声脉冲(PEA)法测量了预压-60 kV/mm电场1 h后,对比研究了六种不同半导电电极材料下交联聚乙烯(XLPE)和MgO/XLPE复合介质中的空间电荷分布;并对不同半导电电极材料下MgO/XLPE复合介质中的平均电荷密度进行了计算。对比实验表明:配方不同的半导电电极材料确实对试样中空间电荷的分布以及空间电荷量影响很大;以乙烯醋酸乙烯共聚物(EVA)为基础材料、添加30wt%炭黑的第二种半导电材料对MgO/XLPE复合介质中空间电荷的抑制效果最好。     

基于α松弛分析CB/LDPE纳米复合介质空间电荷特性

分别以导电炭黑(C-CB)和绝缘炭黑(I-CB)作为纳米填充相,研究不同性能炭黑(CB)对低密度聚乙烯(LDPE)空间电荷特性的影响。采用多种测试方法对CB微观形貌和表面化学特性进行表征。利用电声脉冲(PEA)法测量LDPE及其纳米复合介质的空间电荷分布,并结合动态机械分析法(DMA)和热刺激电流法(TSC)探索CB改善LDPE空间电荷特性的作用机理。结果表明:C-CB比I-CB具有更长的链状结构和较少的表面基团,可与LDPE产生更强的相互作用;C-CB/LDPE和I-CB/LDPE纳米复合介质均能够有效地抑制空间电荷积聚,其中前者的空间电荷抑制能力更强。分析认为复合介质空间电荷性能改善是由于CB与LDPE相互作用,减少了参与α松弛的分子形成的缺陷数量,降低了LDPE内的陷阱密度。     

纳米颗粒形状对线性低密度聚乙烯纳米复合介质电学性能的影响

初步研究了纳米颗粒的形状对纳米复合介质电学性质的影响。以不同形状的纳米氮化硼(BN)为填料,制备了填充分数介于0.5%~2.0%的线性低密度聚乙烯(LLDPE)纳米复合介质,测试了纳米氮化硼在LLDPE中的分散行为、复合介质的结晶和熔融行为、复合介质的宽频介电频谱、空间电荷行为以及直流击穿强度。结果发现,纳米氮化硼的形状对复合介质电学性质的影响在击穿强度方向尤为突出,片状纳米氮化硼复合介质的击穿强度高于LLDPE,而球状纳米氮化硼复合介质的击穿强度低于LLDPE。纳米氮化硼的形状对复合介质的结晶和熔融行为、介电常数和介电损耗角正切等的影响可以忽略。两种纳米氮化硼均可起到抑制空电荷注入的作用,且复合介质中空间电荷衰减速率降低。片状纳米氮化硼复合介质中更易积累界面电荷,导致复合介质内部出现明显的空间电荷振荡分布。     

纳米MgO/环氧复合电介质的空间电荷特性研究

环氧复合材料在高温高场等复杂的工况下易积聚空间电荷，造成局部场强畸变，严重时将引发局部放电乃至绝缘击穿。通过纳米MgO颗粒与环氧树脂（EP）混合制备不同掺杂率的纳米MgO/EP复合电介质，采用差示扫描量热分析（DSC）测试环氧复合电介质的玻璃化转变温度；采用热刺激去极化电流法（TSDC）拟合计算环氧复合电介质的陷阱特性；采用电声脉冲法（PEA）测试环氧复合电介质的空间电荷特性。结果表明：纳米MgO颗粒的添加可以提高环氧树脂的玻璃化转变温度，抑制环氧树脂内空间电荷积聚。随着纳米MgO掺杂率的增加，纳米MgO/EP复合电介质的玻璃化转变温度先上升后下降，深陷阱能级和密度均先增大后减小；空间电荷密度先下降后上升，电场畸变的变化趋势与空间电荷的变化趋势相似。当纳米MgO掺杂率为3%时，纳米MgO/EP复合电介质的玻璃化温度达到最大值，抑制空间电荷积聚和场强畸变的能力最好。     

DC conduction and electrical breakdown of MgO/LDPE nanocomposite

To understand basic electric properties of nano-sized magnesium oxide (MgO) / low-density polyethylene (LDPE) nanocomposite under DC voltage application, the volume resistivity, the space charge distribution and the breakdown strength were investigated. By the addition of nano-sized MgO filler, both the DC breakdown strength and the volume resistivity of LDPE increased. At the average DC electric field of about 85 kV/mm and more, a positive packet space charge was observed in LDPE without MgO nano-filler, whereas a little homogeneous space charge was observed in MgO/LDPE nanocomposite material at the front of electrode. From these results, it is confirmed that the addition of MgO nano-filler leads to the improvement of DC electrical insulating properties of LDPE.     

低密度聚乙烯/纳米蒙脱土复合材料的水树枝生长特性

低密度聚乙烯是高压电力电缆的主要绝缘材料,水树枝生长特性与聚乙烯高压电力电缆绝缘击穿具有紧密联系。采用熔融插层复合法制备了一种低密度聚乙烯/蒙脱土纳米复合材料;设计制作了纳米复合材料的水树枝老化试样及试验装置,在试验中观测了试样的水树枝生长长度,并对试样的水树枝引发率进行了统计,分析了低密度聚乙烯/蒙脱土纳米复合材料的吸水率对水树枝生长的影响;采用差示扫描热法分析了试样的结晶度和晶粒尺寸均匀性,通过分析低密度聚乙烯/蒙脱土纳米复合材料的结晶行为,说明了纳米蒙脱土对纳米复合材料中水树枝的抑制机理。试验与分析结果表明:掺杂质量分数为3%的纳米蒙脱土粒子能够有效地提高低密度聚乙烯的结晶度,使晶粒尺寸分布均匀,吸水率减小,延缓水树枝在低密度聚乙烯中的引发与生长。     

A consideration of potentials of low‐density polyethylene using metallocene catalyst as insulator for power cable

We investigated the high‐field conduction, DC and impulse breakdown strength, space charge distribution, and tree inception voltage for three kinds of new low‐density polyethylene (LDPE) prepared using a metallocene catalyst (mLna, mLao, mLldao), linear LDPE prepared using a Ziegler catalyst (LLao), and LDPE prepared by a high‐pressure process (LDna). The dc and impulse breakdown strengths of LDPEs prepared using a metallocene catalyst were higher than those of LLao and LDna. The high‐field currents of LDPEs prepared using a metallocene catalyst were lower than those of LLao and LDna. A homo‐space charge was accumulated near the cathode in mLna. The tree inception voltage of mLna was higher than that of LDna. From these results, it is concluded that LDPE prepared using a metallocene catalyst has electrical insulating properties superior to the conventional LDPE and that the former has potential as a power cable insulator. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 139(4): 17–25, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.1164     

Space charge trapping in electrical potential well caused by permanent and induced dipoles for LDPE/MgO nanocomposite

Space charge accumulation in low-density polyethylene film containing a small amount of MgO nanoparticles (LDPE/MgO nanocomposite film) subjected to an electric field greater than 100 kV/mm has been studied using an improved pulsed electroacoustic (PEA) system. No marked space charge accumulation was observed in LDPE/MgO nanocomposite films. To determine the mechanism of no space charge accumulation in the LDPE/MgO nanocomposite film, we compared electric potential wells produced by a permanent dipole moment such as that of carbonyl groups (C=0) and an induced dipole consisting of MgO nanoparticles (spherical dielectrics) under a high electric field to create a trapping site for electric charge carriers. The trapping depth created by the permanent dipole moment such as that of the carbonyl groups (C=0) of chemical defects is approximately 0.45 eV. However, the potential well induced by high-permittivity dielectric nanoparticles (MgO) is about 1.5 to 5.0 eV, which is much deeper than that induced by chemical defects. The suppression of space charge formation is explained using the potential well model consisting of a dipole induced by a high-permittivity dielectric nanoparticle. We explained the suppression mechanism of charge accumulation in the LDPE/MgO film that contains deep traps.     

CB/LDPE纳米复合材料的空间电荷抑制特性

采用熔融共混法制备了纯低密度聚乙烯(LDPE)试样和纳米炭黑(CB)颗粒质量分数分别为0.01%、0.03%、0.05%、0.07%的CB/LDPE复合试样。采用扫描电子显微镜观察纳米CB颗粒在LDPE基体中的分散性,并利用电声脉冲法(PEA)测试各试样在常温和-40 kV/mm条件下的空间电荷积聚特性和陷阱特性,讨论纳米CB颗粒提升LDPE基体空间电荷抑制特性的机制。结果表明:相较于纯LDPE试样,CB/LDPE复合试样的空间电荷积聚特性得到了显著改善,其中CB质量分数为0.03%的CB/LDPE复合试样具有最佳的空间电荷抑制效果。纳米CB颗粒提高了复合试样内部的深陷阱密度,这是提高复合试样空间电荷抑制能力的关键。     

Space charge formation and breakdown in polyethylene influenced by the interface with semiconducting electrodes

This paper deals with the influence of interface between polyethylene and semiconducting electrode on the space charge formation and electrical breakdown. Low‐density polyethylene (LDPE) films attached with different semiconducting electrodes were subjected to the DC breakdown test, and corresponding space charge distribution was measured. A heat treatment to LDPE itself did not bring about a significant change in space charge profile; however, when a semiconducting electrode was hot‐pressed, the impurities would migrate into LDPE at high temperature, leading to the change in space charge profile. Furthermore, it was suggested from the comparison between the results with degassed and as‐received semiconducting electrodes that some carriers relating to impurities in the electrode would move into LDPE under the voltage. In addition, it was shown that the breakdown is not determined by the field at the cathode which can supply sufficient electrons, but by the maximum field across the specimen, suggesting that an increase in conduction current due to the generation and/or injection, rather than the electronic avalanche process, leads to the breakdown. © 2001 Scripta Technica, Electr Eng Jpn, 138(3): 19–25, 2002