From LDPE to XLPE: Investigating the change of electrical properties. Part II. luminescence

Luminescence experiments have been used to probe the nature of trapping sites and the dynamic behavior of charge carriers in low density polyethylene (LDPE), antioxidant containing LDPE (LDPE+AO) and cross-linked polyethylene (XLPE). It is shown that deep traps of different natures are present in these materials. For example carbonyl functions provide deep traps in LDPE. New traps are seen in LDPE+AO and XLPE, associated with the anti oxidant itself or with its reaction produces, and to the by-products of the cross-linking reaction. Among those, acetophenone, cumyl alcohol and /spl alpha/-methylstyrene cannot account for the observed spectra. It is shown, in addition, that two XLPE compounds based on two different base resins exhibit the same behaviour demonstrating that the chemical and/or structural modifications introduced by the cross-linking process itself control the charge storage in XLPE. The electrical properties of the same materials are discussed in the light of the work reported in pt.I see ibid., vol.12 no.3 p.438-46, (2005).     

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.     

The effect of low-molecular-weight species on space charge andconduction in LDPE

We have investigated the effect of low-molecular mass species on the space charge behavior such as space charge distribution and electrical conduction of LDPE (low density polyethylene). We also attempted to explain the relationship between the space charge distribution and electrical conduction. The heterocharge, conduction current and effective charge mobility decreased when the low-molecular-mass species in LDPE was removed. It was found that the decrease in conduction current was related to the decrease of heterocharge in LDPE     

Electrical properties of silane crosslinked polyethylene incomparison with DCP crosslinked polyethylene

The electrical properties such as water tree length, electrical conduction, ac breakdown strength and space charge of silane crosslinked polyethylene (SXLPE) were investigated, with a purpose to compare this material with ordinary dicumyl peroxide (DCP) crosslinked polyethylene (XLPE). Experimental results show that SXLPE has a smaller water tree length, much lower conduction current density, a little bit higher ac breakdown strength than XLPE, and on SXLPE only a very small homocharge is seen. The better behaviour of SXLPE under electric stress is attributed to the absence of residual curing byproducts present in XLPE and the change of chemical structure by grafting and curing reactions     

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。     

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).     

Polarization and dielectric behavior of ac-aged polyethylene

High field polarization and dielectric relaxation behavior have been used to study the aging mechanisms of crosslinked polyethylene (XLPE) and low density polyethylene (LDPE) aged at constant alternating electrical field stress in a humid environment at room temperature. For this study, the dielectric spectroscopy data in the frequency range of 10^-5 to 10⁶ Hz and their comparative analysis, have been used to provide electrical analog models of the aging. The dielectric data in the frequency range of 10^-5 to 5×10 ^-2 Hz were calculated from the desorption current, whereas bridge measurements provide the data in the frequency range of 10 Hz to 10⁶ Hz. In addition, thermal transient current and thermally stimulated discharge current measurements have been carried out in order to determine the polarization and space charge accumulation in ac aged polyethylene. A correlation has been observed in the behavior of polarization and dielectric relaxation in the present work. The dielectric behavior of the XLPE cable samples and of the LDPE flat samples show a presence of both the inter-cluster (low frequency) charge exchange and the intra-cluster (high frequency) charge motion, the former mechanism becoming more dominant as the aging progresses. For the XLPE cable samples ac aged in a humid environment at room temperature, relaxation peaks obeying the fractional power law have been observed in addition to a quasi-dc process     

Study of space charge accumulation in polyolefins submitted to acstress

The aim of the present study was to follow space charge formation under ac field (50 Hz) in polyolefins. The thermal step method was used, and charge accumulation was observed in crosslinked polyethylene (XLPE), very low density polyethylene (VLDPE), isotactic polypropylene (PP) and a PE /PP copolymer, the temperature varying from 45 to 90°C. It was found that the amount of charge accumulated under ac conditions may reach a maximum value at a given temperature, while the highest space charge was found in the polyolefin with the lowest crystallinity ratio. The conduction current characteristics of XLPE specimens show the existence of traps in the polymer at a level deeper than the potential barrier electrode/dielectric, explaining the accumulation of injected charge in the material. The injection and conduction mechanisms observed were interpreted by Schottky and Poole-Frenkel processes and used to explain the maximum accumulation of charge occurring at certain temperatures     

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     

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。     

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     

Study of space-charge characteristics in polyethylene for power cable insulation by laser-induced pressure-pulse technique

By utilizing the laser induced pressure-pulse (LIPP) technique, the behavior of space charge in low-density polyethylene (LDPE) and crosslinked polyethylene (XLPE) films in contact with metal or carbon-loaded semiconducting layers was studied quantitatively to clarify the space-charge characteristics in power cables. Negative heterospace charge near the anode and positive space charge in the bulk were observed in unoxidized LDPE under the fields above 120 kV/mm. The amount of negative space charge increased with applied field, while positive space charge in the bulk disappeared with increasing applied field. This indicates that electron injection and ionization are enhanced by applied field. Prominent negative homospace charge was formed near the cathode in oxidized LDPE, which indicates that oxidation enhanced electron injection. The depth of charge centroid from the cathode became larger with increasing temperature. This indicates that the effective electron mobility increases with temperature. Negative space charge also was formed in the bulk in XLPE films with metal electrodes, which indicates that crosslinking enhanced electron injection. XLPE films with a carbon-loaded semiconducting layer showed both negative and positive homospace charges near the semiconducting layers, which indicates that both electrons and holes were injected from the semiconducting layer.     

Deep trapping centers in crosslinked polyethylene investigated bymolecular modeling and luminescence techniques

Space charge in crosslinked polyethylene (XLPE) has been detected under both ac and dc fields. Its role in electrical aging and breakdown is recognized, but not deeply understood. It is thought that identification of the trapping centers in this material would help improve the modeling of conduction and electrical aging as well as making possible the design of crosslinked materials with improved properties. We have developed theoretical and experimental approaches to this problem which emphasize the role of chemical traps acting as deep trapping centers. Molecular modeling is used to estimate the trap depth for negative and positive charge carriers associated with the main by-products of crosslinking reactions (using dicumyl peroxide as a crosslinking agent) since their aromatic structure makes them candidates for deep traps. Calculations on acetophenone, n-methyl styrene and cumyl alcohol show that they indeed can act as deep traps. Because such deep traps can act as recombination centers, their involvement in charge trapping can be checked in specially designed luminescence experiments. In our experiments, charges of both polarities are generated at the surface of the material under study by using a non-reactive cold plasma in helium. The analysis of the decay kinetics and emission spectrum of the subsequent luminescence allows us to define unambiguously the time range in which charge recombination is the dominant excitation process of the luminescence. The emission spectra obtained within this time range provide the optical fingerprint of chromophores acting as deep traps in the material. The low-density polyethylene (LDPE) doped with crosslinking byproducts and XLPE (film and cable peeling) have been investigated. Their role in charge trapping is apparent in the luminescence experiments and in space charge distribution analysis. In thermally treated XLPE, it is shown that other species strongly bonded to the polymer chain are also able to trap electrical charges     

High‐field electrical properties of new LDPE films prepared using metallocene catalyst

Now low‐density polyethylene (M‐LDPE) prepared using metallocene catalyst has narrower composition distribution and molecular weight distributions than linear low‐density polyethylene (LLDPE) using Ziegler catalyst. The authors compared the electrical insulating properties of M‐LDPE films and conventional LLDPE films. The high‐field current of M‐LDPE was found to be lower than that of LLDPE. The difference in current increased with the decrease of temperature. The high‐field current was much reduced in M‐LDPE with a low melting point. The impulse breakdown strength of M‐LDPE increased with the decrease of temperature. The insulating properties of M‐LDPE with a low melting point were improved at 30 °C. These results were explained by the fact that M‐LDPE with a low melting point includes more low‐molecular‐weight components. We also discuss the effects of antioxidant on the electrical properties of M‐LDPE. We compared the electrical conduction and breakdown strength of undoped M‐LDPE and antioxidant‐doped M‐LDPE. Differences in their electrical properties were minor. It was found that the excellent properties of M‐LDPE do not depend on the effects of antioxidant. © 1999 Scripta Technica, Electr Eng Jpn, 130(2): 1–9, 2000     

High‐field electrical properties under AC voltage application in acetophenone‐coated LDPE film

This paper deals with the effects of acetophenone coating on dielectric properties such as tan δ and capacitance and on space charge formation up to electrical breakdown under AC voltage application in low‐density polyethylene (LDPE) film. The existence of acetophenone at the electrical interface enhances tan δ. tan δ in acetophenone‐coated specimens increased with electric field and decreased with the frequency in the high‐field and high‐temperature region. AC breakdown test revealed that the electric strength in noncoated specimens was higher than in acetophenone‐coated specimens, and that the electric strength also decreased with temperature. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 142(3): 1–7, 2003; Published online in Wiley InterScience (www.interscience. wiley.com). DOI 10.1002/eej.10086     

茂金属聚乙烯改善低密度聚乙烯的介电性能

针对高压、超高压直流塑料电缆中存在的空间电荷效应,大多数直流电力电缆常采用改性方法提高其介电性能,如空间电荷特性、体积电阻率和击穿强度等。常用的改性方法主要有添加剂、共混、接枝和二元共聚4种。共混技术较广泛用以改性聚乙烯电缆,提高其介电性能。因此用电声脉冲法(PEA)测量了MPE与LDPE共混试样中的空间电荷分布;用高阻计测量了共混物的体积电阻率,用阶梯电压测量了共混物的交流击穿场强。试验结果表明,1%MPE与LDPE共混能有效降低空间电荷效应,提高交流击穿场强7.9%,略降低体积电阻率。最后讨论了共混物的物质结构、电荷陷阱及介电性能间的关系。     

茂金属聚乙烯改性低密度聚乙烯中电荷入陷与传输特性

聚合物的电性能与其物理、化学、微观结构密切相关.通过电声脉冲(PEA)法测量少量茂金属聚乙烯(MPE)与低密度聚乙烯(LDPE)共混物在不同场强作用下的去极化特性.根据空间电荷限制电流(SCLC)理论,通过公式推导求解共混物平均电荷体密度、视在迁移率、陷阱深度分布及阈值场强.结果表明,1%MPE与LDPE共混,能有效减少深陷阱密度,增加浅陷阱密度,提高电荷迁移率和阈值场强.     

交流电压下基于空间电荷效应的XLPE电缆绝缘老化研究现状

交联聚乙烯(XLPE)电缆以其优良的机械和电气性能广泛应用于现代电力系统。研究表明,在直流电压作用下绝缘中容易形成空间电荷,导致电场畸变,加速绝缘老化。国内外很少关于交流电压下空间电荷对XLPE电缆绝缘影响的研究。本文综述了交流电压下空间电荷对XLPE电缆绝缘老化的影响及其作用机理,并介绍了交流电压下测量空间电荷分布的改进的电声脉冲法。结果表明,交流电压下,空间电荷分布特性影响XLPE电缆绝缘老化。     

A general review of polymeric insulation for use in HVDC cables

The authors present a review article of the properties of XLPE and an examination of the origins of space charge and how it is measured. The space charge in the insulation and the conduction current can affect the electric stress distribution in the insulation. The effect of morphology on the electrical properties of polyethylene is discussed in detail.     

Understanding treeing phenomena and space charge effect in gamma-irradiated XLPE cable insulation

In the present work, electrical trees were experimentally generated in virgin and gamma-irradiated XLPE cable insulation, under AC voltages. Fibrillar type of electrical tree structure forms from the defect site in gamma-irradiated specimens. Failure times due to electrical trees were analysed by adopting Weibull distribution studies. The results of the study indicate that gamma-irradiated specimens, where the rate of tree propagation is high, causing early failure of insulation. Pulsed electro acoustic emission (PEAE) technique was adopted to understand the space charge formation in XLPE cable insulation. The results of the study indicate that homo and hetero charges form near to the electrodes especially in gamma-irradiated XLPE cable insulation. Variations in space charge density at different voltage magnitudes with time were analysed. It is observed that the electric field in the insulating material becomes highly non-uniform on occurrence of hetero charges. It is also realized that on removal of applied voltage, the charge decay is less with gamma-irradiated specimens. Based on the present study, it could be concluded that Space charge density in insulating material and life of insulating material due to electrical tree formation shows inverse relationship.