Effect of mechanical loading on the kinetics of electrical breakdown in polymers

The decrease in the electrical lifetime (time of expectation of a breakdown in an electric field of constant polarity) under tensile loading of disoriented polyethylene, Teflon, and lavsan films in the range of 100–300 K is studied. It is found that tensile loading decreases the depth of intermolecular electron traps due to an increase in the spacing of chain molecules in amorphous regions of polymers. This accelerates the hopping (from one trap to another) transport of electrons, leading to the formation of critical (breakdown) volume charges.     

Features of the kinetics of electrical damage of polymers

The kinetics of electrical damage (breakdown) of polymer films 20–50 μm thick in a constant-sign field of 0.5–0.6 GV/m at 77–300 K has been studied. At elevated temperatures (250–300 K), the exponential temperature dependence of the durability and the above-barrier thermal-fluctuation mechanism of electron emission from traps, i.e., space charge accumulation leading to breakdown, take place. At low temperatures (77–200 K), there are separate local decreases in the durability (minima) at the athermal durability level. The identity of the temperatures of durability minima and measured thermoluminescence maxima of polymers was found. A conclusion is made about the mechanism of thermally stimulated tunneling (subbarrier emission) of electrons from traps.     

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     

Dielectric and electrical properties of polymorphic bismuth pyrostannate Bi2Sn2O7

The Bi₂Sn₂O₇ compound existing simultaneously in two polymorphic modifications, namely, orthorhombic and cubic, has been synthesized for the first time by solid-phase synthesis. The dielectric and electrical properties of the compound have been studied in the temperature range 100 K < T < 500 K. Anomalies in the temperature dependences of the electrical resistivity and the permittivity (imaginary and real parts) have been found at both low and high temperatures. These features are explained in terms of the model of martensitic phase transitions.     

Structural phase transitions in Fe3+ -doped ferroelectric TlGaSe2 crystal

This paper presents the results of dielectric constant and Electron Paramagnetic Resonance (EPR) investigations of Fe³⁺-doped TlGaSe₂ single crystals in the temperature range of 15–300 K. The influence of Fe impurities on dielectric properties and phase transitions of TlGaSe₂ crystal has been studied. The results were considered in comparison with earlier observed results from pure TlGaSe₂ compounds. We observed the considerable decrease of the dielectric constant as well as the change of the shape of the temperature dependence of the dielectric constant in doped crystals. Some certain significant changes of EPR spectra, which are associated with a strong splitting and appearance of additional resonance lines, were observed at the temperatures below 110 K. Such transformations are considered as the result of non-equivalent displacements of different groups of Tl atoms during the structural phase transitions.     

Electrical and thermoluminescence properties of γ-irradiated La2CuO4 crystals

Abstract

Measurements of the electrical properties of unirradiated as well as γ-irradiated La₂CuO₄ crystals were carried out at different temperatures in the frequency range of 0.1-100 kHz. Thermoluminescence (TL) studies were also performed on such crystals in the temperature range of 300-600K. The conductivity of the unirradiated La₂CuO₄ crystals were found to obey the power law frequency dependence at each measured temperature below the transition temperature (T_c = 450K). The activation energies for conduction and dielectric relaxation time have been calculated. The TL response and the dc resistance were found to increase with γ-irradiation dose up to 9-10 kGy. The results showed that the ferroelastic domain walls of La₂CuO₄ crystal as well as its TL traps are sensitive to γ-raditaion. This material can be used in radiation measurements in the range 225 Gy-10 kGy.     

Luminescence in photoconducting zinc telluride

The photoluminescent spectrum of ZnTe: Ga: Zn has been obtained over a range of temperatures from 323 to 4·2°K. Two prominent emissions are observed. One is due to an isoelectronic oxygen center and the other is due to two transitions, both involving a deep impurity level located about 0·6 eV from the conduction band. Such deep minority-carrier traps are consistent with those found in other highly photosensitive II–VI compounds.     

Magnetic properties, magnetoresistance, and magnetic-field-induced phase transitions in Tb0.95Bi0.05MnO3 and Eu0.8Ce0.2Mn2O5 multiferroics

This paper reports on a study of the magnetic properties, magnetoresistance, and phase transitions in the semiconducting manganite multiferroics Tb_0.95Bi_0.05MnO₃ and Eu_0.8Ce_0.2Mn₂O₅ whose dielectric properties have been a subject of an earlier study. An analysis of these properties has led us to the conclusion that the above crystals at temperatures T ≥ 180 K undergo phase separation with the formation of a dynamic periodic alternation of quasi-2D layers of manganese ions in different valence states, i.e., charge-induced ferroelectricity. This state exhibits a giant permittivity and ferromagnetism in the layers containing Mn³⁺ and Mn⁴⁺ ions. At low temperatures (T < 100 K), the phase volume is occupied primarily by the dielectric phase. Studies of the magnetic properties and the effect of the magnetic field on the dielectric properties of crystals substantiate the scenario of the formation of a state with giant permittivity put forward by us. At low temperatures, Tb_0.95Bi_0.05MnO₃ exhibits features at the points of phase transitions in pure TbMnO₃. A ferromagnetic moment is observed to exist at all the temperatures covered. At the boundaries of the quasi-2D layers, magnetic-field-induced jumps of the electrical resistivity caused by metamagnetic transitions in the layers with Mn³⁺ and Mn⁴⁺ ions are observed. At temperatures T ≥ 180 K, the electrical resistivity undergoes a periodic variation in a magnetic field which is a manifestation of carrier self-organization. A high magnetic field is capable of shifting the phase transition from 180 K to higher temperatures and inducing additional phase transitions.     

Electrical properties and dielectric relaxation of thermally evaporated zinc phthalocyanine thin films

The electrical transport properties and dielectric relaxation of Au/zinc phthalocyanine, ZnPC/Au devices have been investigated. The DC thermal activation energy at temperature region 400-500 K is 0.78 eV. The dominant conduction mechanisms in the device are ohmic conduction below 1 V and space charge limited conduction dominated by exponential trap distribution in potentials >1 V. Some parameters, such as concentration of thermally generated holes in valence band, the trap concentration per unit energy range at the valence band edge, the total concentration of traps and the temperature parameter characterizing the exponential trap distribution and their relation with temperatures have been determined. The AC electrical conductivity, σ_ac, as a function of temperature and frequency has been investigated. It showed a frequency and temperature dependence of AC conductivity for films in the temperature range 300-400 K. The films conductivity in the temperature range 400-435 K increased with increasing temperature and it shows no response for frequency change. The dominant conduction mechanism is the correlated barrier hopping. The temperature and frequency dependence of real and imaginary dielectric constants and loss tangent were investigated.     

High–pressure electrical conductivity and Raman spectroscopy of chalcanthite

Abstract

The phase transitions and dehydration of chalcanthite were investigated by electrical conductivity and Raman spectroscopy at 1.0–24.0?GPa and 293–673?K in a diamond anvil cell. At ambient temperature, two secondary phase transitions were observed according to discontinuous changes in the slope of Raman shifts, full width at half maximum and electrical conductivities at ～7.3 and ～10.3?GPa. The dehydration temperatures were determined by the splitting of Raman peaks and changes in electrical conductivity as ～350 and ～500?K at respective ～3.0 and ～6.0?GPa. A positive relationship for chalcanthite between dehydration temperature and pressure is established.     

Specific Features of the Structure and the Dielectric Properties of Sodium–Bismuth Titanate-Based Ceramics

The phase formation, specific features, and the dielectric properties of the ceramics of compositions from the region of morphotropic interface in the (Na_0.5Bi_0.5)TiO₃–BaTiO₃ system modified by Bi(Mg_0.5Ti_0.5)O₃ and also low-melting additions KCl, NaCl–LiF, CuO, and MnO₂ that favor the control of the stoichiometry and the properties of the ceramics have been studied. The ceramics are characterized by ferroelectric phase transitions that are observed as jumps at temperatures near 400 K and maxima at T_m ~ 600 K in the temperature dependences of the dielectric permittivity. The phase transitions at ~400 K demonstrate the relaxor behavior indicating the existence of polar domains in the nonpolar matrix. An increase in the content of Bi(Mg_0.5Ti_0.5)O₃ favor a decrease in the electrical conductivity and dielectric losses of the samples, and the relative dielectric permittivity at room temperature ε_rt is retained quite high, achieving the highest values ε_rt = 1080–1350 in the ceramics modified with KCl.     

Proton spin lattice relaxation in single crystal of NaH3(SeO3)2

Proton spin lattice relaxation time in NaH₃(SeO₃)₂ was measured at temperatures 300-77 K at a frequency of 8.01 MHz. Except near the temperatures of the ferroelectric transitions at 196 and 100 K the relaxation rate is governed by paramagnetic impurities, and the formula derived by Blumberg for diffusion-limited case is applicable. A logarithmic divergence above 196 K is related to the anomaly of the dielectric constant in the same temperature range.     

Phase transitions and metastable states in TlGaSe2

The results of measurements of the dielectric constant of TlGaSe₂ in temperature range of successive phase transitions are presented. An anomaly in the temperature dependence of the real part of dielectric constant in TlGaSe₂ has been observed at about 242?K in addition to anomalies at 115, 108, and also near 65?K as reported in previous publications. The presence of temperature hysteresis effects in temperature interval between 115 and 242?K allowed making a conclusion about possible existence of an incommensurate phase in the mentioned temperature range. A model of succession of the structural phase transitions in TlGaSe₂ has been suggested.     

CdSe在高压下的电学性质及相变

 利用在金刚石压砧上集成的微电路,原位测量了CdSe多晶粉末在温度为300~450 K、压力达到23 GPa时电阻率随温度和压力的变化关系。实验结果表明：在加压过程中,电阻率在2.6 GPa压力时出现的异常改变,对应着CdSe从纤锌矿向岩盐矿结构的转变,而在6.0、9.8、17.0 GPa等压力处出现的电阻率异常,则是由CdSe中的电子结构的变化所引起的;在卸压过程中,只在约14.0和3.0 GPa压力下观察到了两个电阻率异常点。通过对电阻率随压力变化曲线的模拟,得出了CdSe高压相的带隙随压力的变化关系,据此预测CdSe金属化的压力应在70~100 GPa之间。变温实验结果表明,在实验的温度和压力范围内,CdSe的电阻率均随温度的增加而升高。     

Mechanical relaxation in radiation-polymerized vinyl stearate

Mechanical relaxation studies, over the temperature range from about 100[ddot] K to or above the melting point, were performed on unannealed and annealed samples of vinyl stearate, on as-received and purified samples of poly(vinyl stearate), and on a series of radiation-polymerized samples having different monomer-polymer ratios. These latter samples were polymerized in the solid state by exposure of the crystalline monomer to a ⁶⁰Co source and were characterized by density measurements, X-ray diffraction, and differential thermal analysis (DTA). The modulus-temperature and loss-temperature curves of the monomer showed a mechanical relaxation centered at 210[ddot]K (959 Hz) which appeared to decrease toward a limiting value with increase of annealing time. This behavior is similar to that observed in dielectric studies of vinyl stearate. With increase of radiation time and greater conversion to polymer, the magnitude of the 210[ddot] K loss peak increased while the peak position shifted to lower temperatures. The loss-peak is located at 172[ddot] K (864 Hz) in the polymer and is analogous to the γ -relaxation peak in polyethylene in height, breadth, and temperature location. It is attributed to local reorientational motions of (side-chain) —CH₂— segments in disordered or defect regions. X-Ray and DTA data indicate that solid solutions of the monomer and polymer are present in many of the radiation-polymerized samples. The effects of large radiation exposures on the relaxation behavior of the polymer were examined and compared with similar data on polyethylene. The implications of the current data concerning molecular interpretations of the polyethylene relaxations are discussed.     

Electronic transport mechanisms in tetraphenyleprophyrin thin films

Thermally-evaporated thin films of tetraphenylporphyrin, TPP, with thickness range from (175 to 735) nm had been prepared. Annealing temperatures ranging from (273–473) K do not influence the amorphous structure of these films. The influence of environmental conditions: film thickness, temperature and frequency on the electrical properties of TPP thin films had been reported. It was found that dc conductivity increases with increasing temperature and film thickness. The extrinsic conduction mechanism is operating in temperature range of (293–380) K with activation energy of 0.13 eV. The intrinsic one is in temperatures >380 K via phonon assisted hopping of small polaron with activation energy of 0.855 eV. The ac electrical conductivity and dielectric relaxation in the temperature range (293–473) K and in frequency range (0.1–100) kHz had been also studied. It had been shown that theoretical curves generated from correlated barrier hopping (CBH) model gives the best fitting with experimental results. Analysis of these results proved that conduction occurs at low temperatures (300–370) K by phonon assisted hopping between localized states and it is performed by single polaron hopping process at higher temperatures. The temperature and frequency dependence of both the real and imaginary parts of dielectric constant had been reported.     

Mechanisms of elementary events in the kinetics of electrical breakdown of polymer and ceramic dielectrics

The kinetics of electrical breakdown of thin (15–70 μm) layers of polymers and ceramics in a constant-sign field at 77–480 K has been investigated. The temperature dependences of the longevity (breakdown waiting time) of both dielectrics have been found to be similar to each other. At elevated temperatures, the longevity of the dielectrics varies exponentially with increasing temperature, and at reduced temperatures, it is temperature-independent (there is an athermal plateau). The mechanisms of elementary events controlling the process of preparation of the dielectrics for breakdown at elevated and reduced temperatures are the thermal-fluctuation over-barrier electron transition from trap to trap and the tunneling (under-barrier) transition, respectively. The hopping electron transport in the field direction gives rise to critical space charges causing breakdown of the dielectrics. The transition barrier heights (trap depths) have been determined. The low-temperature longevities of the polymer and the ceramic have been found to be similar, whereas the transition barrier for the ceramic is much higher than that for the polymer and the applied field in the former case is significantly (by a factor of tens) lower than that in the latter case. Electron traps in the polymer are adequately described by the Coulomb center model, whereas this is not the case for the ceramic.     

The p–T phase diagram of KNbO3 by a dielectric constant measurement

A dielectric constant measurement was carried out on perovskite-type ferroelectrics KNbO₃ over a wide range of temperature under high pressure. The temperature- and pressure-dependence of the dielectric constant clarified that all temperatures of the transitions from the ferroelectric rhombohedral to orthorhombic, to tetragonal and then to the paraelectric cubic phase, decrease with increasing pressure. These results indicate that the orthorhombic–tetragonal transition takes place at 8.5 GPa and the tetragonal–cubic transition at 11 GPa, at room temperature.     

直流老化对CaCu3Ti4O12陶瓷介电性能的影响

在电场为3.5 kV/cm的条件下, 对CaCu₃Ti₄O₁₂陶瓷进行了60 h的直流老化, 研究了老化过程对CaCu₃Ti₄O₁₂陶瓷介电性能和电气特性的影响. J-E特性测试结果表明, 直流老化导致CaCu₃Ti₄O₁₂陶瓷击穿场强、非线性系数和势垒高度明显降低. 介电性能测试结果表明, 低频介电常数和介电损耗明显增大, 并且介电损耗随频率的变化遵从Debye弛豫理论, 可分解为直流电导损耗和弛豫损耗, 直流老化主要导致了电导损耗的增加. 在低温233 K, 介电损耗谱中出现两个弛豫峰, 其活化能分别为0.10, 0.50 eV, 认为对应着晶粒和畴界的弛豫过程, 且不随直流老化而变化. 通过电模量谱对CaCu₃Ti₄O₁₂陶瓷的弛豫过程进行了表征, 发现直流老化导致的界面空间电荷在外施交变电场的作用下符合Maxwell-Wagner极化效应, 并在低频区形成新的弛豫峰. 在高温323-473 K的阻抗谱中, 晶界弛豫峰在直流老化后明显向高频移动, 其对应的活化能从1.23 eV 下降到0.72 eV, 晶界阻抗值下降了约两个数量级. 最后, 建立了CaCu₃Ti₄O₁₂陶瓷的阻容电路模型, 分析了介电弛豫过程与电性能之间的关联.     

温度对聚酰亚胺直流击穿特性与闪络特性影响的研究

随着超导技术的迅速发展,高温超导电力设备的工作温度已经可以控制在液氮温度附近,绝缘材料的电气特性是影响电力设备工作性能和运行可靠性的重要因素。聚酰亚胺由于其优异的电气性能和力学性能,广泛应用于常温下电力设备绝缘,而其作为低温绝缘材料应用的研究目前鲜有报道。因此,在液氮温度下聚酰亚胺的绝缘性能研究具有十分重要的意义。文中选取室温附近(300K)和液氮温度(78K)两个温度点,对聚酰亚胺的直流击穿性能和沿面闪络特性进行了测试。研究结果表明温度对聚酰亚胺绝缘材料的直流击穿场强和沿面闪络强度均有一定影响。