用光刺激放电法研究纳米粉末掺杂低密度聚乙烯中陷阱能级

通过光刺激放电(PSD)技术研究了纳米粉末掺杂低密度聚乙烯(LDPE)中的陷阱能级.利用连续扫描法得到了不同掺杂比例的Al₂O₃,MgO纳米粉末掺杂试样以及相同掺杂比例的多种纳米粉末掺杂试样的PSD电流谱,定性地得出了试样陷阱能级的深浅变化.分步扫描法定量地描述了LDPE试样在Al₂O₃纳米掺杂前后陷阱能量分布的变化.结果表明,掺杂比例大于0.2%的Al₂O₃纳米粉末掺杂、大于0.5%的MgO纳米粉末掺杂能够显著地使得LDPE陷阱能级变深.结合纳米掺杂对LDPE空间电荷注入影响的相关报道,可推测纳米掺杂对空间电荷注入的抑制与试样中陷阱能级变深存在密切的关联.     

Influence of oxidation on space charge dynamics in DC aged low-density polyethylene

In this study, low-density polyethylene (LDPE) samples were aged under different oxygen concentration (0, 20%, and 50%). The ageing was implemented with an average external DC electric field of 50 kV/mm at 40 °C for 1000 h. It was found that augmentation of charge accumulation and suppression of charge dissipation were enhanced with increasing of oxygen concentration. The capture capability of trap sites got stronger with higher oxygen contents, which could be attributed to oxidation product newly generated during DC ageing. These trap sites acted as trap centers to capture the injected carrier while it was on the way towards the opposite electrode and decrease the apparent mobility. FTIR absorption spectra showed that new elements between 1680 and 1750 cm^?1 corresponding to ketone and aldehyde occurred due to oxidation. The bipolar charge injection model was implemented to simulate space charge transport in aged LDPE samples. It was shown that more carriers were captured and the traps gradually filled up when the oxygen concentration in the ageing test increased. A higher oxygen concentration seemed to result in a deeper average trap depth, which increased the amount of trapped charge because it was not easy to detrap. These simulation result corresponded to the experimental measurement.     

Transient dynamics of packet-like space charge in low-density polyethylene at high temperatures

Among features observed in polyethylene-based materials under high fields, packet-like space charge are frequently reported but without complete theory explaining their formation and propagation. The present contribution reports transient dynamics of packet-like space charge in low-density polyethylene (LDPE) under multi-field coupling conditions based on pulsed electro-acoustic (PEA) method. The measurements were carried out under −125 kV/mm at 20 °C, 40 °C, and 60 °C. Space charge results reveal systematic occurrence of positive packet-like space charge in all samples generated at the anode and then moved toward the cathode. It is observed that higher temperatures contribute to the migration of packet-like space charge and field distortion. Based on the detailed injection model of packet-like space charge, it is shown that electrode injection plays a major role in the formation of positive packet-like space charge, the total amount and depth not only depend on the temperature, but also the negative charges dynamics. Packet-like space charge phenomena at different temperatures still feature NDM relationship with the nonlinear increase of migrate velocity as the rise of temperature.     

掺杂含量对环氧纳米复合电介质陷阱与空间电荷的影响

环氧纳米复合电介质具有抑制空间电荷积聚、高电阻率、高击穿强度等优异性能,对直流电力设备的发展具有重要的作用.但纳米粒子含量对纳米复合电介质陷阱、电导率和空间电荷的影响机理尚不清楚.本文在纳米复合电介质交互区结构模型的基础上提出了计算交互区浅陷阱和深陷阱密度的方法,得到了浅陷阱和深陷阱密度随纳米粒子含量的变化关系.随着纳米粒子含量的增加,浅陷阱密度逐渐增大,深陷阱先增加然后由于交互区重叠的影响而逐渐减少.研究了纳米粒子含量对浅陷阱控制载流子迁移率的影响,发现随着纳米粒子的增多,浅陷阱大幅增多,浅陷阱之间的平均间距迅速减小,导致载流子更容易在浅陷阱间跳跃迁移,浅陷阱控制载流子迁移率增大.建立了纳米复合电介质的电荷输运模型,采用电荷输运模型计算研究了环氧/二氧化钛纳米复合电介质的空间电荷分布、电场分布和电导率特性.发现在纳米粒子添加量较小时,交互区的深陷阱对电导的影响起主导作用;纳米粒子添加量进一步增加,浅陷阱对电导的影响将起到主要作用.     

Dielectric relaxation and ac conductivity behavior of carboxyl functionalized multiwalled carbon nanotubes/poly (vinyl alcohol) composites

We study the dielectric relaxation and ac conductivity behavior of MWCNT-COOH/Polyvinyl alcohol nanocomposite films in the temperature (T) range 303–423 K and in the frequency (f) range 0.1 Hz–1 MHz. The dielectric constant increases with an increase in temperature and also with an increase in MWCNT-COOH loading into the polymer matrix, as a result of interfacial polarization. The permittivity data were found to fit well with the modified Cole-Cole equation. Temperature dependent values of the relaxation times, free charge carrier conductivity and space charge carrier conductivity were extracted from the equation. An observed increment in the ac conductivity for the nanocomposites was analysed by a Jonscher power law which suggests that the correlated barrier hopping is the dominant charge transport mechanism for the nanocomposite films. The electric modulus study revealed deviations from ideal Debye-type behavior which are explained by considering a generalized susceptibility function. XRD and DSC results show an increase in the degree of crystallinity.     

Local electrical overstressing in polymer dielectrics

Using a spherical concentric capacitor as a microspike model, the electric field distribution in a polymer dielectric material with shallow and deep electron traps is investigated. It is established that in the course of field emission from microspikes on the electrode and space charge accumulation on the traps, the values of coefficient of electric overstresses depend on temperature, injection barrier height, and trap concentration and depth in the polymer material. The behavior of this coefficient is characterized as a function of the mean field strength. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 3–9, December, 2008.     

基于类耿氏效应的低密度聚乙烯中空间电荷包行为的模拟仿真

低密度聚乙烯材料中的空间电荷包现象通常会引起严重电场畸变而影响其击穿特性. 本文借鉴半导体中的耿氏效应的负微分迁移率机理来描述电荷包的形成机理,并结合载流子的注入条件及体内陷阱对电荷迁移的影响等因素,对文献中报道的两类外加场强不同且迁移趋势各异的空间电荷包行为进行了模拟仿真,模拟的电荷包大小随电场变化规律,电荷包迁移速率随时间变化规律等与相应实验结果符合.模拟结果表明,产生耿氏效应的负微分迁移率是造成电荷包非弥散传输的主要原因,其与材料电极注入情况及体内陷阱态的共同作用导致了空间电荷包行为迁移的多样性. 关键词： 空间电荷包 耿氏效应 模拟仿真 负微分迁移率     

Effect of humidity in charge formation and transport in LDPE

Charge distribution and transport have been investigated in LDPE films with different humidity content under electric fields up to 130 MV/m. Pulsed electroacoustic measurements showed that, as water content increases, positive charge packets formation in the anode is enhanced and they propagate toward the cathode with higher transit speeds. Fits of surface potential decay measurements showed that charges in dry samples are injected directly into the volume, but the presence of moisture generates new trap centers in the surface of the material. This new trap level causes a charge accumulation on the surface, that gradually passes into the bulk. The observed behavior in development and propagation of charge packets are explained according to these results. Thermally stimulated depolarization current measurements showed a non-distributed relaxation associated to the new trap levels on the surface of the wet samples.     

聚乙烯空间电荷包行为的形成机理与仿真方法研究

聚乙烯中的空间电荷包行为是空间电荷的一种特殊的输运行为.研究表明,空间电荷包行为由于受材料本身特性、外加电场大小以及环境温度等的影响,导致其产生过程及传输特性上存在较大差异,这些因素给空间电荷包行为产生机理研究带来了较大困难.通过对电荷的电极注入过程、载流子的体内迁移规律及空间电荷与体内陷阱的相互作用机制进行分析,探讨了不同外加电场及不同深度陷阱能级对电荷包行为造成的相关影响,在此基础上建立物理模型来描述电荷包的产生和迁移过程.模型中提出了在高于阈值电场时,载流子迁移速度与电场关系存在负微分迁移率的假设.基于此模型对空间包行为的模拟结果与实验结果取得较好的一致. 关键词： 空间电荷包 数值模拟 负微分迁移率     

电场和温度对聚合物空间电荷陷阱性能的影响

模拟分子的结构和行为有助于更深刻地分析空间电荷陷阱性能变化的微观机理.利用Materials studio软件建立聚乙烯模型,通过分子链段运动产生的能量和自由体积变化对微观结构和电荷陷阱进行分析.结果表明:温度由298 K逐渐升高至363 K的过程中,聚合物分子热运动加剧导致的滑移扩散现象,使自由体积和陷阱能级在363 K处分别出现1542.07 ~3和0.66 eV的最大值和最小值.然而在Z轴方向施加0.0007 Hartree/Bohr(1 Hartree/Bohr=5.2×10~(11)V/m)电场作用时,由于电致伸缩产生Maxwell应力,使分子链段出现局部有序排列,增大范德瓦耳斯能至-360.18 kcal/mol(1 kcal/mol=4.18 kJ/mol),而自由体积降低了279.77 ~3,导致陷阱能级减小0.45 eV.当363 K和0.0007 Hartree/Bohr联合作用时,聚乙烯的陷阱能级相比同温无电场作用降低0.17 eV.分子模拟结果与实测结果相符.利用分子热运动和电致伸缩效应,初步探讨了材料自由体积和范德瓦耳斯相互作用能变化的微观机理,证实分子链段运动改变了微观结构,从而影响电荷陷阱特性.并且与温度相比,电场作用会使材料产生更低能级的空间电荷陷阱.     

Effect of ground electrode on charge injection and surface potential of corona charged polyethylene film

The surface potential decay measurement is a simple and low cost tool to assess electrical properties of insulation materials; therefore, understanding the physical mechanisms of the surface potential decay becomes necessary. With our recent space charge measurement results on corona charged samples, bipolar charge injection on corona charged samples had been observed. Based on this new fact, it is anticipated that the ground electrode should have significant effect during corona charging and subsequently decay processes. In the paper, low density polyethylene (LDPE) film with gold ground electrode was compared with LDPE film with aluminium ground to study effect of ground electrode on charge injection and surface potential decay processes. Charging current during the corona charging, surface potential decay and space charge dynamics after corona charging in the samples with either gold coated or aluminium ground electrode were measured. Differences have been observed for gold ground electrode when compared with aluminium ground electrode. Higher work function of gold electrode is responsible for the observed differences. A preliminary simulation has also attempted to show that the bipolar injection may take place in corona charged LDPE films.     

Pre-stressing effect on DC breakdown in low-density polyethylene

Polyethylene is widely used in electrical wires and power cables. The pre-stressing effect, which restricts the applications of polyethylene, has not yet been investigated in depth. We studied the breakdown of low-density polyethylene (LDPE) films pre-stressed by direct current (DC) electric field. The results showed some conformity, as reported in many other papers, that the DC breakdown strength E_B+ with the same polarity to that of the pre-stressing field was higher than the DC breakdown strength E_B of thin LDPE films without pre-stressing, while the DC breakdown strength E_B? with the opposite polarity was lower than E_B. Such phenomena could be explained by the hetero effects of accumulating space charges, which enhanced the electrical field when the polarity was reversed. However, as a further increase in pre-stressing electrical field, both E_B+ and E_B? were found higher than E_B. We investigated the space charge behavior in LDPE films and found that when applied with a higher electrical field, space charge packet initialized and traveled through the specimen. The results suggest that the space charge packet behavior may contribute to the pre-stressing effects on electrical breakdown in LDPE films.     

聚合物材料空间电荷陷阱模型及参数

采用电声脉冲测量技术研究了直流电场下低密度聚乙烯材料的电荷入陷和脱陷特征. 发现在不同电场周期下样品的电荷衰减呈现不同的特征, 为此提出了一个简单的基于两陷阱水平的入陷和脱陷模型, 并计算了相应的参数, 如陷阱能级和密度. 确定了不含任何添加剂的低密度聚乙烯样品中存在的两种水平的陷阱能级分别为: 较浅陷阱能级0.77–0.81 eV 对应的浅陷阱电荷密度为(1.168–1.553)× 10¹⁹ m^-3; 较深陷阱能级0.96–1.01 eV 对应的深陷阱电荷密度为(1.194–4.615)× 10¹⁸ m^-3. 最后初步验证了材料的深陷阱能级和对应的深陷阱电荷密度随老化而增加, 可考虑将模型中的两能级陷阱参数作为老化诊断特征参量. 关键词： 聚合物 空间电荷 陷阱 老化     

线型离子阱中空间电荷效应的理论分析

线型离子阱中的离子在射频场作用下做宏观的久期运动,久期运动频率与实验参数有关.但当离子阱中囚禁大量同种电荷的离子时,空间电荷效应会导致离子间存在相互排斥的库仑力,使离子的运动频率发生漂移.本文通过求解泊松方程计算了空间电荷产生的附加电场的解析表达式,在小振动近似下理论计算了该附加电场对久期运动频率的影响,模拟了不同离子云中心密度下久期频率的漂移,讨论了离子云的数目、温度与实验参数之间的关系.对用离子阱进行的频标实验、碰撞实验和其他方面的研究都具有重要的指导意义.     

Effect of epitaxial crystallization on packet-like space charge characteristics in low-density polyethylene under multi-field coupling conditions

In order to study the effect of epitaxial crystallization on charge transport in low-density polyethylene (LDPE) under multi-field coupling conditions, three typical epitaxial crystallizations, namely disorder (glass substrate), crossover (isotactic polypropylene substrate), and parallel (polytetrafluoroethylene substrate), were prepared and denoted as LD-G, LD-iPP, and LD-PT, respectively. Packet-like space charge through samples was analyzed by the pulsed electro-acoustic (PEA) method. It is shown that different microscopic surface morphologies appeared in the LDPE samples with different epitaxial crystallizations, which, however, do not change the crystalline structure of the bulk. Packet-like space charge phenomena were observed and the distortion field increased with the temperature which could be attributed to the larger amount of charge injection in a shorter period. The differences of the amount and injection rate of the space charge were explained and verified considering the typical chain alignment of epitaxial crystallization, which, in our opinions, contributes to the pass over of positive charge in LD-iPP samples.     

Electric field involved transport at elevated temperature in nanocrystalline silicon carbide nitride (nc-SiCN) thin films for harsh environment applications

The present study represents a systematic temperature dependent charge transport and dielectric properties of nanocrystalline silicon carbide nitride (nc-SiCN) thin films grown on Pt/Ti/SiO₂/Si substrate. A large negative temperature coefficient of resistance (TCR) ranging from 6200 to 2300 ppmK^-1 in the temperature range 300–773 K, suggests that the nc-SiCN thin films could be useful for futuristic thermal-based sensors. The current density vs. electric field (J-E) characteristics was measured at different temperatures (300–673 K). Detailed J-E analysis revealed an ohmic conduction at the low applied electric field (<65 kV/cm) within the entire temperature range. However, at high electric field (>65 kV/cm), space charge limited conduction (SCLC) mechanism was found to be dominating in low measurement temperature (300–473K), whereas, a transition from SCLC mechanism to Poole-Frenkel mechanism was observed with further increment in the temperature beyond 473 K. The temperature invariant dielectric tunability (n_r ∼10%) and low zero electric field leakage current density (J ∼10⁻⁷A/cm²) at 673 K temperature, demonstrates the feasibility of nc-SiCN thin films for tunable device applications in the high-temperature and harsh environment.     

单层有机器件的电子传输特性的数值模拟

在漂移扩散模型的基础上建立了单层有机器件的模型,包括了电荷注入、传输、空间电荷效应和陷阱的影响.电荷注入考虑了热电子发射电流和隧道电流.模拟得到的结果和文献中报道的实验测试数据一致.模拟研究了各个因素对器件J-V曲线的影响,电流和器件长度成反比,电流随着空穴注入势垒的减小而增加.电子注入势垒从1.7 eV减少到0.5 eV时,电流随着电子注入势垒的减小而减小,这主要是因为有机材料中电子迁移率太小,电子注入电流的增加可以忽略,而电子注入势垒的减小使内建势增加,在同样的电压下,场强 关键词： 有机器件 传输特性 数值模拟     

以能带理论诠释直流聚乙烯绝缘中空间电荷的形成和抑制机理

高压直流塑料交联聚乙烯电缆的研发难点是消除其中的空间电荷效应. 目前, 国内外学者普遍通过添加纳米粒子在聚乙烯体内形成深陷阱捕获电荷的机理来抑制电荷积聚, 但此抑制机理违背了电场的基本理论. 以能带理论全面阐述聚合物介质中空间电荷的形成和抑制机理, 从一级陷阱模型出发, 应用电荷入陷和脱陷动力方程, 推导了聚合物介质中空间电荷的形成过程. 在聚合物介质中引入深陷阱后, 介质Fermi能级位移, 电极与介质之间界面接触由Ohm接触转变为阻塞接触. 考虑到无定形相中大量的陷阱密度, 电荷耗尽区宽度小于100 Å, 电极与介质之间的界面对电子变得透明, 形成中性接触, 在电压作用下, 这种聚乙烯介质中不再可能形成空间电荷. 最后, 在纯聚乙烯和纳米改性后含有深陷阱的聚乙烯两种试样上, 分别测量了电导与电场强度的关系和空间电荷分布曲线, 实验结果符合理论推导. 关键词： 直流绝缘 能带理论 空间电荷 抑制机理     

An analytical method for DC negative corona discharge in a wire-cylinder device at high temperatures

This paper proposes an analytical solution for DC negative corona discharge in a wire-cylinder device based on experimental results in which both the corona and drift regions are considered; this approach aims to provide a theoretical method for analyzing electrostatic precipitation at high temperatures. The inter-electrode space is divided into three zones, namely, the ionization layer, the attachment layer (corona region) and the drift region, to investigate the space charge concentration and the electric field distribution. The boundary of the ionization layer is assumed to be the radius at which the rate of ionization balances that of electron attachment. The radius where the value of E/N equals 110 Td is recommended as the boundary of the attachment layer. It was determined that an increasing temperature leads to a decrease in the largest space charge number density and the largest electric field in the drift region that can be provided by a discharging device. With respect to the device in the present work, when the temperature increases from 350 °C to 850 °C, the largest electric field decreases from ∼9 × 10⁶ V/m to ∼3 × 10⁶ V/m, and the largest charge number density decreases from ∼1.3 × 10¹⁵ m⁻³ to 6.4 × 10¹⁴ m⁻³. The radius of the corona region, the space charge number density and the electric field increase as the applied voltage increases at a given temperature. For example, at a temperature of 550 °C, when the applied voltage increases from 10,500 V to 18,879 V, the radius of the corona region increases from ∼2.9 mm to ∼4.9 mm. It appears to be unreasonable to use a constant value that is calculated from Peek's formula as the electric field at the surface of the cathode under all of the conditions.