高导热绝缘高分子复合材料的研究进展

介绍了高导热绝缘高分子复合材料的导热机理,讨论了影响高导热绝缘高分子材料导热性能的主要因素,阐述了高导热绝缘高分子材料的发展方向。     

Application of a novel polypropylene to the insulation of an electric power cable

Cross‐linked polyethylene (XLPE) has been widely adopted as insulating material for high‐voltage power cables up to 500 kV. Further improvement of electrical and thermal properties on insulating material is required in order to increase cable operation efficiency. Therefore, the development of novel insulating material possessing high thermal properties will be necessary. Recent progress of catalysis technology contributes to obtain new polymeric materials which may be applied to electrical insulation. The authors investigated the basic properties of newly developed stereoregular syndiotactic polypropylene (s‐PP) which is synthesized with homogeneous metallocene catalyst. Though recycling of cross‐linked polymers such as conventionally used XLPE may be difficult because of their poor heat deformation, the s‐PP which is not cross‐linked must be suitable for recycling. A series of experiments on its physical and electrical properties gave the following results.

• (1) s‐PP has sufficient flexibility compared with isotactic polypropylene (i‐PP ).
• (2) Both AC and lightning impulse breakdown strength of s‐PP in spite of no cross‐linking are superior to those of XLPE in the temperature range from 25 to 90 °C.
• (3) Degradation by copper of s‐PP is less than that of i‐PP.
• (4) s‐PP/VLDPE blend shows sufficient brittleness temperature for use.

These results suggested that s‐PP should serve as insulating material for power cables at higher‐temperature operation. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 146(1): 18–26, 2004; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002//eej.10210     

Novel electrical and optical properties of liquid conductingpolymers and oligomers

A conducting polymer with highly extended conjugated bonds in its main chain becomes fusible and also soluble in common solvents after the introduction of long side chains, such as alkyl, as a substituent. Because these liquid conducting polymers and oligomers have much smaller band gaps than those of conventional organic liquids, they exhibit relatively high electrical conductivity and also interact with visible light. Therefore, these liquid conducting polymers can be used effectively for fundamental research to clarify the electronic state and transport processes in dielectric liquids. Novel anomalies in electrical conductivity, photoconductivity and luminescence also have been observed in these liquids, and are discussed in terms of the fluctuation of electronic band gap and the interchain interaction, which depends on alkyl side chain length and on its conformation, and therefore on temperature. The unique applications of these liquid conducting polymers and solutions are also discussed. Characteristics of the interface between conducting polymer and dielectric liquids are also found and discussed in terms of electron scavenging of CO₂ in liquid and CO₂ fixation     

碳纳米管填充的高介电常数聚合物基复合电介质材料

介绍了碳纳米管电性能及其功能化改性、以及利用碳纳米管掺杂聚合物制备柔性高介电常数复合材料的研究现状,发现化学气相沉积法得到的多壁碳纳米管(MWNT)在化学处理前后形成的聚合物基复合材料具有明显不同的分散特性和介电性能.相对于微米级球形导电颗粒填充的复合材料,一维尺度碳纳米管填充的复合材料具有明显低得多的渗流阈值,低渗流阈值可以明显保持聚合物基体优良的机械性能.期望在这一领域从工程电介质的角度做深入的研究工作,以发现碳纳米管在聚合物基复合材料领域所表现出的新特性、新现象.     

导电聚合物电催化剂的研究进展

综述了导电聚合物作为低温燃料电池催化剂载体和电催化剂的研究进展,主要介绍了导电聚合物的导电机理、催化剂的制备方法及催化性能。针对导电聚合物电催化剂化学降解严重、缺乏单体电池性能测试等缺点,展望了发展的方向。     

聚合物绝缘材料表面陷阱与电致发光现象研究

聚合物材料老化前会出现电致发光现象，其紫外分量可能导致材料的劣化。因此电致发光的研究可为分析材料老化和击穿机理提供依据。该文首先基于等温电流衰减理论，设计了材料表面陷阱参数测量装置，实验中采用多针电极对低密度聚乙烯(polyethylene，LDPE)、聚丙烯(polypropylene，PP)和聚四氟乙烯(polytetrafluoroetylene，PTFE)3种材料进行表面充电，记录表面电位衰减并按照等温电流衰减理论计算得到材料表面陷阱参数。结果显示，LDPE的陷阱密度较PTFE和PP大，LDPE和PTFE的电子空穴陷阱分布成对称结构，PP的电子陷阱密度明显大于空穴陷阱密度，这与材料的分子结构的对称性有密切关系。同时基于单光子计数模块设计了微弱发光数据采集系统，对上述材料在真空中交流电压下的电致发光特性进行了测量和分析。材料的陷阱密度对其电致发光特性具有重要的影响，材料的陷阱密度越高，发光越弱，反之则越强。     

Polyethylene under electrical stress

Fifty years ago, the concept of an intrinsic electric strength for insulating solids was fashionable. It was supported by the sophisticated theoretical models of von Hippel, Frohlich and others for the interaction of electrons with crystal lattices in an electric field. The models came to be applied, rather implausibly perhaps, to polymers such as semi-crystalline polyethylene (PE). In that climate, the work of van Roggen on the high-field conductivity of single lamellar crystals of PE was notable. Since then, the picture of the insulating properties of PE has had to be painted with an increasingly complex palette in which the electrical elements have had to be supplemented by mechanical, chemical, and optical ones. The present review of the conducting properties of the polymer considers these other features, but concludes that the fundamental characteristics of the lamellar PE crystal are still the determining factors.     

锂离子电池富硫聚合物正极材料的研究进展

综述了锂离子电池富硫聚合物正极材料的研究进展.侧重介绍了利用单质硫对聚合物进行加热硫化,制备具有电化学活性的导电高分子锂离子电池正极材料的方法.所制备的材料具有较高的比容量(超过600mAh/g),且循环性能优良.聚合物硫化是制备低成本锂离子电池有机正极材料的有效方法.     

Conduction mechanisms and high-field effects in syntheticinsulating polymers

The absorption and conduction currents in synthetic insulating polymers, viz., polyethylene, polypropylene, polyethylene-terephthalate and polyvinylidenefluoride, with dc fields may be electronic or ionic both and it may be difficult to determine their origins unambiguously. The charges which are present in the bulk of the polymer may be responsible for both the absorption and the conduction current. A limited displacement of charges together with the rotation of side chains may provide a decaying transient current in the presence of an externally impressed field whereas the conduction current may originate from a hopping of charge carriers in which the charges transfer between localized states. The complex dielectric response of these polymers with ac field may also be explained by intra- and inter cluster charge movement which would be consistent with the unified model, stated above for the case of dc fields     

New technique for the fabrication of conductive polymer/insulating polymer composite films

The electrochemical polymerization of pyrrole on an ITO (indium‐tin oxide)‐coated glass electrode with an insulating film of poly(vinyl alcohol), PVA, produces a flexible composite polymer film with electrical, optical, and electrochemical properties very similar to polypyrrole (PPy). The rate of electrochemical polymerization depends on the diffusion of the electrolyte across the PVA film to the ITO electrode. In particular, hydrophilic solvents easily penetrate into the PVA film. By applying this new process, we demonstrate a unique method of forming electrically conductive patterns in PVA film. It will be possible to develop electrodes for electrical stimulation of the nervous system using a conducting polymer, PPy. By a similar technique we have fabricated poly(3,4‐ethylenedioxythiophene), PEDOT/PVA, composite films and have investigated their electrochemical basic properties. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(4): 1–8, 2011; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.21055     

Measurement of the internal space charge distribution of ananti-electrostatic discharge polymer

Charged dielectrics can cause an electrostatic discharge (ESD) that damages electronic circuits because of the electromagnetic noise associated with the discharge. Newly developed anti-ESD polymers are expected to be `anti-ESD polymer insulating materials', but the mechanism of their action against ESD has not been explained. Since the anti-ESD polymers contain some kind of polymer solid electrolyte, they should be able to be characterized by the behavior of their internal space charge. By measuring the space charge distribution of an anti-ESD polymer using the pulsed electroacoustic method under DC electric field, we found that the polymer was effective in preventing ESD because the internal space charge near the surface partially compensates the electric field of the external charge on the surface. We also found indications that the internal space charge behavior is related to the dispersion of the polymer solid electrolyte     

DC electrical treeing phenomena and space charge

Influence of space charge on dc tree propagation is studied using many insulating polymer materials under divergent fields. The inception voltage and the propagation of dc treeing are affected strongly by space charge. Space charge formation in polymers was observed directly by using thermally stimulated current (TSC) techniques under divergent field. These results of the space charge effect on dc treeing phenomena are consistent with those obtained by the TSC method. From these results, the origin of space charge in polymers and the suppression techniques for space charge formation were discussed     

FEATURE ARTICLE Conducting Polymer Composites

Conducting polymer composites become increasingly important for technical applications. In this article, the resulting electrical properties of such materials are illustrated by a variety of experimental examples. It is shown that the combined mechanical, thermal and electrical interaction between the filler particles via their electrical contacts and the surrounding polymer host matrix are responsible for the properties of the composite material. A short review is given of the theoretical background for the understanding of the electrical transport in such materials. The arrangement of the filler particles and the resulting conductivity can be described either by percolation or by effective medium theories. It can also be related to different types of charge carrier transport processes depending on the internal composite structure. Special emphasis is given to the microstructure of the filler particles such as size, hardness, shape and their electrical and thermal conductivities. A detailed analysis of the physics of the contact spots and the temperature development during current flow at the contact is given. It is shown that the polymer matrix has a strong influence on the electrical conductivity due to its elastic properties and the response to external thermal and mechanical stimulation. Strong changes in the electrical conductivity of conducting polymer composites can be realized either by thermal stimuli, leading to a positive and negative temperature coefficient in resistivity, or by applying mechanical stress. By using nonlinear fillers an additional degree of functionality can be achieved with conducting polymers.     

Surface flashover of oil-immersed dielectric materials in uniform and non-uniform fields

The applied electrical fields required to initiate surface flashover of different types of dielectric material immersed in insulating oil have been investigated, by applying impulses of increasing peak voltage until surface flashover occurred. The behavior of the materials in repeatedly over-volted gaps was also analyzed in terms of breakdown mode (some bulk sample breakdown behaviour was witnessed in this regime), time to breakdown, and breakdown voltage. Cylindrical samples of polypropylene, low-density polyethylene, ultra-high molecular weight polyethylene, and Rexolite, were held between two electrodes immersed in insulating oil, and subjected to average applied electrical fields up to 870 kV/cm. Tests were performed in both uniform- and nonuniform- fields, and with different sample topologies. In applied field measurements, polypropylene required the highest levels of average applied field to initiate flashover in all electrode configurations tested, settling at ~600 kV/cm in uniform fields, and ~325 kV/cm in non-uniform fields. In over-volted point-plane gaps, ultra-high molecular weight polyethylene exhibited the longest pre-breakdown delay times. The results will provide comparative data for system designers for the appropriate choice of dielectric materials to act as insulators for high-voltage, pulsed-power machines.     

耐高温绝缘漆的制备及其在玻璃丝包线上的应用

用自制有机硅低聚物与环氧树脂合成环氧改性有机硅树脂,通过添加无机填料和有机助剂制备了耐高温绝缘漆和浸漆玻璃丝包线,并对绝缘漆的性能及影响因素进行了分析。结果表明,所制得的耐高温绝缘漆具有较高的耐热性和较好的柔韧性、附着力,浸漆玻璃丝包线综合性能良好。     

Spectral analysis of optical emission due to isothermal chargerecombination in polyolefins

Light emission from electrically stressed polymers, so called electroluminescence, is a subject of great interest because it is associated with electrical aging and dielectric breakdown of highly insulating materials. Radiative recombination of charge carriers on luminescent centers generally is evoked as the main contribution to the emission, but this is difficult to assess in polyolefins since the spectral features associated with this mechanism are not known. The reason is twofold. First, there is a lack of knowledge on the nature of the luminescent centers in these materials, and second, it is difficult to get wavelength-resolved electroluminescence spectra due to the low light level. By using an alternative activation method, we have isolated the emission spectrum associated with isothermal charge recombination in polyethylene and polypropylene. Electrical charges of both polarities are brought to the surface of the samples by contact with a cold plasma powered at a frequency of ≈5 kHz. The kinetic and spectral features of the recombination-induced emission are recorded after discharge switch off. The recombination mechanism is considered on the basis of the light decay kinetics whereas the chemical nature of the luminescent centers is discussed by a comparison with the photoluminescence spectrum of the polymer. It is shown that charges recombine by tunneling from traps to the luminescent centers which are unsaturated species. The chromophores involved in photo- and recombination-induced luminescence appear to be the same, but not the electronic transitions. Light emitted upon charge recombination has been assigned to transitions from the lowest lying triplet states of poly-enone sequences     

直接甲醇燃料电池中阳极催化剂的研究进展

从铂基合金催化剂、以导电聚合物为载体的复合催化剂和含氮的大环配合物的开发等三个方面重点综述了直接甲醇燃料电池(DMFC)中阳极催化剂的研究进展,同时简要概述了DMFC中甲醇渗透对电池性能的影响及其解决方案。有关研究表明,合金组成、催化剂载体以及大环配合物对阳极催化剂的催化活性和稳定性有着直接的影响。尽管目前已经进行了大量的关于甲醇在阳极催化剂上的作用机理的研究工作,但还未形成共识。另外,利用新的合成方法制备高分散的催化剂也是阳极催化剂发展的重要方向。同时,还须从根本上解决甲醇在Nafion膜中的渗透问题。     

Space charges remaining in polymers after electron beam irradiation and the role of conductivity in their decay profiles

Five typical insulating polymers and a carbon‐loaded polyethylene were irradiated with 200‐keV electrons, and the space charge distributions remaining in the polymers were measured. When the polymer film is short‐circuited after irradiation, the amount of space charge gradually decreases monotonically. By analyzing such decay profiles, it becomes clear that the decay of the charges remaining after the irradiation is governed by the conductivity of the polymer. © 2015 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Charging of deformed semicrystalline polymers observed with ascanning electron microscope

A scanning electron microscope technique is employed to investigate the charging response of stretched semi-crystalline polypropylene (PP) and high density polyethylene (HDPE). The results reveal that the charging response of these insulating polymers varies with the amount of deformation due to stretching. The curves of charging response as a function of extension for HDPE and PP both can be divided into four regions showing up, down, and up and down trends, respectively. These four regions are related to four different deformation stages in the semicrystalline polymers, and polaron formation appears to be appropriate for the interpretation of the charging behavior     

The application of novel polypropylene to the insulation of electric power cable (3)

Having a higher melting temperature than polyethylene, polypropylene has been expected to be an insulation material for power cables. But isotactic polypropylene (i‐PP) used generally is unsuitable as cable insulation because it shows poor flexibility, low breakdown strength due to growing spherulites, and so on. But stereoregular syndiotactic polypropylene (s‐PP) newly developed with metallocene catalyst shows quite different properties than i‐PP. In our previous paper, we investigated the basic properties of s‐PP and the initial properties as a cable which was manufactured using s‐PP insulation. It was revealed that s‐PP had superior thermal and electrical properties to cross‐linked polyethylene and the s‐PP insulation table showed satisfactory initial properties. However, in order to apply to an actual cable, the properties must be maintainable over 30 years after construction. In this paper, we estimated the long‐term remaining properties for s‐PP insulation table. A series of experiments on long‐term properties gave the following results: (1) s‐PP cable shows longer life over 30 years; (2) the breakdown strength of s‐PP cable after a long‐term experiment equal to 30 years is slightly lower than the initial breakdown strength, but it is sufficient as a remaining property. Furthermore, water‐tree resistivity of s‐PP was investigated and it was revealed that s‐PP significantly suppressed the water tree propagation compared with XLPE. These results suggested that s‐PP cable would serve as a next‐generation cable. © 2006 Wiley Periodicals, Inc. Electr Eng Jpn, 155(3): 1–8, 2006; Published online in Wiley InterScience ( www.interscience. wiley.com ). DOI 10.1002/eej.20114