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     

用电子束辐照注入电荷包研究低密度聚乙烯中的电荷迁移率

通过研究外加电场强度50k V/mm以下低密度聚乙烯中的空间电荷包行为,使用一种多层结构的受辐照的双面粘贴聚氟乙烯薄膜低密度聚乙烯样品,通过电子束辐照在样品内部形成"波包"分布,在外加电场强度较低时形成电荷包,使用激光压力波法监测电荷包迁移。结果表明,以电荷包峰值位置为参考点,在样品内实际电场下电荷包平均迁移率分布范围为(0.17~3.01)×10?15m2/(V·s)。通过对不同外加电场强度下的空间电荷包行为的研究得到,电荷包迁移速率与电场强度关系符合负微分迁移率假设模型,从而证明了在较低的电场强度下负微分迁移率模型的正确性。     

Properties of Space Charge Distributions and Conduction Current in XLPE and LDPE under DC High Electric Field

Space charge behavior and conduction current in polyethylene under dc stress were investigated. One of the reasons for the different breakdown property in cross‐linked polyethylene (XLPE) from that in low‐density polyethylene (LDPE) may be based on the existence of cross‐linking by‐products in XLPE. Furthermore, a thermal history in cross‐linking process for XLPE may also cause of the difference. It is generally accepted that the existence of the cross‐linking by‐products increase the conduction current in XLPE under dc stress. It is also said that an anneal treatment in air atmosphere may affect to the electrical properties under dc stress. Therefore, we investigated the effect of the cross‐linking by‐products and the anneal treatment on space charge behavior and conduction current in polyethylene under dc stress. In our research, it is thought that the increasing dissipation power in XLPE is the cause of the breakdown in it under dc stress. Therefore, to calculate the dissipation power in the bulk of test sample, we measured the space charge distribution and the external circuit current simultaneously. Based on the results, we discussed the reason of the difference of the space charge properties in XLPE and LDPE focusing on the cross‐linking by‐products and the oxidation of the test samples.     

Transient phenomena of current and field distortion due to dynamics of packet‐like charges in LDPE films

Simultaneous measurements of space charge and external current were carried out using a PEA measurement system with an electrometer on the back of a grounding electrode in order to clarify the physical situation of a huge packet of positive space charges in LDPE films. A large number of positive charges from a semiconducting anode were accumulated at the interface between LDPE and an Al‐cathode at a mean applied field of 1.5 MV/cm and then finally disappeared. The results of simultaneous measurements showed that the external current kept a relatively high value during charge accumulation and further increased when the charges disappeared. Both the charge dynamics and the external current were restricted by addition of a low‐molecular‐weight paraffin wax, indicating that carrier transport was influenced by the microstructure of the polymer. The dynamics of the residual charges after short‐circuiting is also discussed. © 2012 Wiley Periodicals, Inc. Electr Eng Jpn, 179(4): 10–17, 2012; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.21256     

From LDPE to XLPE: investigating the change of electrical properties. Part I. space charge, conduction and lifetime

This paper discusses the results of space charge, conduction current and electrical lifetime measurements performed on widely-used materials for electrical insulation, that is, low density polyethylene (LDPE) and cross-linked polyethylene (XLPE). Space charge accumulation profiles were compared in LDPE, low density polyethylene plus antioxidant (LDPE+AO) and XLPE, with consideration of thermal treatment effects in LDPE and XLPE. Significant variation (decrease) of accumulated space charge and apparent mobility, as well as slight decrease of conduction current, can be seen going from LDPE to LDPE+AO and XLPE, which may be associated with formation of deeper trap levels (or an increase of their density). On the contrary, electrical life under AC voltage does not show significant differences from LDPE to XLPE. This latter result underlines that life under high AC electrical stress is mostly determined by defects (weak points) rather than material characteristics associated with charge injection and transport.     

Some factors for the space charge formation in polyethylene

Information on space-charge behavior in thick insulated samples aids in understanding the dc characteristics of polymer-insulated dc cables. The pulsed electroacoustic method is used to investigate several space charge formation factors in 2 mm-thick polyethylene (PE). The following results were obtained. For measurement factors: (1) A polymeric semiconducting electrode provides a more accurate measurement than does a metal electrode as a result of better matching of acoustic impedance with PE. (2) Within a dc electrical stress range of several tens kV/mm, the space charge distributions under and after dc voltage application are almost the same; this is due to a comparatively long time of space-charge decay. (3) The space-charge distribution of a plate sample agrees with that of a cable sample having the same insulation thickness. For insulating material factors: (1) The amount of space charge in crosslinked polyethylene (XLPE) is much larger than that in low-density PE (base of XLPE). The space charge of XLPE continues to increase even after dc voltage application (24 h); that of LDPE reaches equilibrium with a few hours. (2) The aforementioned space charge difference between XLPE and LDPE is assumed to be caused by ionic impurities in XLPE, not by the additives themselves (acetophenon and cumylalcohol as byproducts of cross linking and antioxidant).     

氯化聚乙烯共混对聚乙烯的空间电荷效应的影响

在直流电场作用下 ,用电声脉冲法测量了低密度聚乙烯 (LDPE)中空间电荷的分布 ,计算结果表明 ,异极性空间电荷严重畸变试样中的电场的分布。以少量氯化聚乙烯 (CPE)混入低密度聚乙烯中 ,大大降低了试样中的空间电荷 ,电场分布趋向均匀。在正负极性直流预压短路树枝试验中 ,分别提高试样短路树枝起始电压 2 6 8%和 36 3%。通过直流预压和电晕电荷注入后 ,短路过程中空间电荷分布的测量 ,提出氯化聚乙烯的作用机理在于降低了聚乙烯中陷阱的深度和密度。     

Space charge behavior in low-density polyethylene

The space charge distribution in low-density polyethylene (LDPE) was measured with the pulsed electroacoustic (PEA) method. We used three types of LDPE: LDPE-L and LDPE-H were prepared by the high pressure process, and m-LDPE was polymerized with a metallocene catalyst. Space charge in LDPE strongly depended upon the electrode material. Semiconductive electrodes enhanced carrier injection into LDPE and, as a result, space charge. The density, polymerization process, applied field, temperature and so on also affected the space charge behavior. This space charge behavior was compared with the results of dc current measurements     

Measurement of space charge distribution in epoxy resin

Internal space charge behavior of insulating materials has recently attracted attention of many researchers, and a large number of experimental studies were carried out by using the materials for dc cables, such as XLPE, LDPE, and HDPE. Epoxy resins are used for insulation under strong electric fields in power apparatus and in electronic devices, and we investigated the behavior of internal space charge using the pulsed electroacoustic method. Two types of epoxy resins were studied: insulation-grade and craft-grade. When dc electric fields were applied to the craft resins treated by immersing them into room-temperature water for 8 and 24 h, positive and negative charges accumulated near the anode and the cathode, respectively, and the charge distribution changed with the immersion time. On the other hand, no charge was observed in the insulation-grade epoxy resin. Next, we treated the samples by immersing them into 100 °C water for 8 h. When the sample was treated for 8 h, hetero charge distribution, which means positive charges near the cathode and negative charges near the anode, was observed. This result is consistent with a previous paper reporting that by chemical analysis, secondary decomposition had occurred. These results show that water and temperature influence the internal space charge behavior of epoxy resins. © 1999 Scripta Technica, Electr Eng Jpn, 129(3): 9–16, 1999     

Space charge formation in γ-irradiated low densitypolyethylene

Energetic ionizing radiation can alter the chemical structure of polymeric materials and also may give rise to the presence of trapped charge within the material, the trapping characteristics of which may be influenced by these radiation-induced structural alterations. In the present work, the formation of space charge in γ-irradiated LDPE (low-density polyethylene) was investigated using the technique of a LIPP (laser induced pressure pulse). Specimens of LDPE, ~350 μm thick, were irradiated in a ⁶⁰Co γ-source in room air to various doses and the results indicate that space charge distributions are dependent on both dose and electric stress, including the length of time during which the stress is applied. At low doses (⩽10 kGy), there is a large amount of positive charge adjacent to the cathode, leading to stress enhancement at the interface. Higher applied stress serves to extend the positive charge towards the anode. At high doses (⩾50 kGy), the charge distribution is more complicated than that for low doses. Here there is initially negative charge present adjacent to the cathode and a substantial positive charge adjacent to the anode. With the passage of time, however, there is a polarity change from negative to positive at the cathode and a decrease in the density of the positive charge at the anode, with negative charge in the middle of the sample     

Electrodes and charge injection in low-density polyethylene usingthe pulsed electroacoustic technique

The effects of electrode materials on space charge formation in low-density polyethylene (LDPE) have been investigated experimentally using the pulsed electroacoustic (PEA) technique. Common electrode materials used in either the laboratory or power cable industry were selected, i.e. aluminum, gold and carbon loaded crosslinked polyethylene (XLPE), and space charge accumulation after the application of high electric stress was monitored. Experimental results demonstrated that charge injection processes take place in all cases once the applied stress has exceeded a threshold. However the amount of charge, and the polarity of the dominant injected charges showed a significant dependence on the electrode materials under the same applied electric stress     

固体绝缘中空间电荷测量装置的研制和应用

介绍了电声脉冲法空间电荷分布测量装置的测量原理和性能，并利用此装置测量了试样中的空间电荷密度分布，运用有限元法计算空间电荷对试样内部电场的畸变。为了研制超高压直流塑料电缆料，以少量的极性聚合物混炼到低密度聚乙烯中，降低了交联聚乙的空间电荷效应，大幅度提高了５０％直流预压短路树枝的起始电压。     

电极材料对低密度聚乙烯中空间电荷的影响

用电声脉冲法(PEA)测量了不同电极材料对低密度聚乙烯(LDPE)中空间电荷的影响。电极材料为常见的金属,如:铝、含铅黄铜、含锌黄铜和紫铜。实验发现不同电极材料均有空穴和电子注入;并且在实验条件下电极功函数越高越容易注入空穴,功函数越低越容易注入电子;铝(+)/紫铜(-)电极系统能有效减少聚乙烯中的空间电荷注入,进而抑制因空间电荷聚集引起的局部场强过高。     

Space charge behavior in XLPE cable insulation under 0.2-1.2 MV/cmdc fields

This report deals with space charge behavior in PE (polyethylene) under dc fields. Direct observation of time-dependent space charge profiles in 3-mm thick XLPE (crosslinked low-density polyethylene) cable insulation under dc electric fields was performed using the pulsed electroacoustic method. Stable hetero charges were formed when the field was as low as 0.2 MV/cm, and intermittent generation of packet shaped space charges and their propagation through the insulation were observed when the field was as high as 0.7 MV/cm. These phenomena were reproduced in sheet specimens of XLPE and LDPE (low-density polyethylene). It was found that hetero charges resulted from heat treatment of the XLPE specimen containing antioxidant and acetophenone, which is one of the crosslinking by-products, suggesting dissociation of the antioxidant through solvation at high temperature by acetophenone. The packet charges were easily detected when acetophenone was diffused into the LDPE specimen. However, uniformity of acetophenone distribution prevented the packet charge generation. It is suggested on the basis of several experimental results that local ionization of impurities in the insulation through solvation by acetophenone takes place assisted by high field and leads to the packet charge generation. A numerical simulation was carried out based on the above model     

形态对聚乙烯中空间电荷包运动特性的影响

空间电荷相关研究是直流电介质材料特性研究的重要领域,聚乙烯则是主要的内绝缘材料之一。为了对高压直流条件下聚乙烯中的空间电荷现象进行深入研究,应用电声脉冲法空间电荷测量系统对高场强下低密度聚乙烯中的空间电荷现象进行测量,观察到了空间电荷包现象。研究结合不同热处理方法得到了不同微观形态的聚乙烯试品,并在不同场强下结合微观形态的变化对低密度聚乙烯的空间电荷包运动速率进行了分析。结果表明,聚乙烯的微观形态对空间电荷包特性有显著的影响,也对空间电荷包运动速率有明显的影响,结晶度越高,空间电荷包运动速率越小。     

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。     

油纸绝缘介质的空间电荷积聚与消散特性

油纸材料的绝缘问题在换流变压器、直流套管、直流电缆等高压大型直流设备大量应用的情况下显得十分突出。为探讨高压直流设备绝缘的最主要问题—空间电荷效应,应用电声脉冲法(PEA)对油纸绝缘材料的空间电荷特性进行了研究。有关外加场强对油纸材料中空间电荷积聚情况的影响和在较高场强下油纸材料的击穿破坏与空间电荷关系的研究结果表明:①低场强下油纸材料中空间电荷以电离产生为主;而在较高场强下,先后在阴极和阳极产生了同极性载流子注入。②相对于聚乙烯而言,由于油纸材料的电导率较大,材料内的空间电荷在外加电场撤去后很快消散。③空间电荷的注入和运动会导致油纸材料的劣化和破坏。油纸材料中的空间电荷快速消散现象有利于直流设备在极性反转条件下的运行,为阐释油纸绝缘良好的长期性能提供了有重要意义的试验依据。     

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     

±320kV直流电缆交联聚乙烯/三元乙丙橡胶附件击穿特性

高压直流电缆接头与终端为电缆系统故障的多发点,其击穿强度为直流输电系统安全稳定运行的重要基础。文中以±320 kV高压直流海底电缆中交联聚乙烯(cross linked polyethylene,XLPE)/三元乙丙橡胶(ethylene propylene diene monomer,EPDM)附件为研究对象。首先,研究电缆及附件负荷循环耐压试验,发现附件界面为击穿薄弱环节;其次,研究绝缘材料电导率随温度变化特性对电场分布的影响规律,通过有限元仿真模拟电缆空载和满载运行时附件的温度分布与电场分布,发现最大电场出现在电缆绝缘靠近附件应力锥一侧,为29.5 kV/mm,低于附件材料的击穿场强;最后,研究界面在直流电场下空间电荷特性对电场分布规律的影响,通过电声脉冲法测试复合叠层片状样品介质界面的空间电荷及其电场分布,发现场强畸变率约为100%~200%。同材料本征绝缘匹配相比,界面空间电荷积聚对附件内部电场造成的畸变程度更严重,在后续附件提升中应更注重开发抑制空间电荷的绝缘材料。     

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。