炭黑/硅橡胶介电弹性体复合材料的制备研究

硅橡胶介电弹性体因其模量低、应变响应速度快、回弹速率高及温度适应范围广等优点在介电弹性体研究领域广受关注,具有十分广阔的应用前景。但其存在介电常数低、电致变形量小的缺点。针对此问题,本研究以硅橡胶为基体,以炭黑为填料,通过将炭黑质量分数变化范围控制在0%~20%,厚度变化控制在0.5mm~2mm,制备了炭黑/硅橡胶介电弹性体复合材料,并对其力学性能和介电性能进行测试。结果表明:在硅橡胶基体中添加炭黑填料,通过改变加入的炭黑质量分数,提高了介电常数,并使介电损耗保持在一个较低范围。在控制材料厚度时发现,厚度为1.5mm 时,复合材料的断裂强度较大,同时弹性模量相对较低,这有利于材料发生变形。     

Dielectric behavior of some aromatic polyimide films

Aromatic polyimides were prepared by polycondensation reaction of two aromatic diamines, such as 4,4′-diaminodiphenylmethane (DDM) and 3,3′-dimethyl-4,4′-diaminodiphenylmethane (MDDM), with aromatic dianhydrides, such as 4,4′-isopropylidene-diphenoxy-bis(phthalic anhydride) (6HDA), benzophenonetetracarboxylic dianhydride (BTDA) and hexafluoroisopropylidene-bis (phthalic anhydride) (6FDA). These polymers are soluble in polar aprotic solvents and can be cast into thin films from such solutions. The polyimides show high thermal stability, with decomposition temperature being above 430 °C in air, and high glass transition temperature being in the range of 200–287 °C. The free standing films, having the thickness of tens of micrometers, exhibited good mechanical and electrical insulating properties. The dielectric constant, molecular mobility and AC conductivity of thin films prepared from these polymers were investigated in detailed. The study of their dielectric behavior evidenced low dielectric constant values, in the range of 2.88–3.48 at 1 Hz at room temperature, and three relaxation processes (γ,β₁ and β₂) were observed at sub-glass temperatures for polyimides based on 6HDA and 6FDA and only two (γ and β) relaxations were detected for polyimides based on BTDA. The cooperativity of the molecular motions associated with the relaxation processes was discussed.     

Ag+ ion transport studies in a polyvinyl alcohol-based polymer electrolyte system

Thick films of pure polyvinyl alcohol and polyvinyl alcohol doped with silver nitrate with different compositions have been prepared by solution cast technique. The FT-IR spectrum confirms the complexation process. The conductivity of the pure polyvinyl alcohol is of the order of 10⁻⁷ Sm⁻¹ at 90 °C, and its value increases by two orders of magnitude when doped with 20 wt% of AgNO₃. The activation energy, calculated from the Arrhenius plot for all compositions of the poly vinyl alcohol doped with silver nitrate, is between 0.24 and 0.35 eV. The migration energy for the ion in polymer electrolyte has been calculated from the modulus spectrum, and is in good agreement with the activation energy calculated from the Arrhenius plot. The modulus spectra indicate the non-Debye nature of the material.     

Synthesis,characterization, optical,thermal and electrical properties of polybenzimidazoles

The variation of dielectric constant and dielectric loss of two novel polybenzimidazole (PBI) were studied at constant temperature with variable frequency. The polymers have shown maximum dielectric constant at low applied frequency 50 Hz at 393 K due to the space charge polarization. The AC conductivity and activation energy of polymers were arrived from dielectric constant and dielectric loss values. PBIs were synthesized by the oxidative polycondensation of benzimidazole monomers, 2-(1H-benzo [d] imidazole-2-yl)-4-bromophenol (BIBP), and 2-(1H-benzo [d] imidazole-2-yl)-6-methoxyphenol (BIMP) in an aqueous alkaline medium using NaOCl as oxidant. The monomers and polymers were characterized by various spectroscopic techniques. Fluorescence spectra of monomers and polymers showed their λ _max emission in the region of 472–479 and 463–472 nm respectively. The electrical conductivities of iodine doped polybenzimidazoles were measured by four-point probe technique and it increases with increase in iodine vapour contact time. The electrical conductivity values were correlated with the charge density on imidazole nitrogen obtained from Huckel calculation method. Both the PBI are having reasonably good thermal stability and are shown by high carbines residues of around 40% at 500°C in thermogravimetric analysis.     

Dielectric,impedance and excitation performance of Aurivillius oxides: Bi4Pb2Zr2TiFeNbO18

The Aurivillius phase-based composition bearing chemical formula Bi₄Pb₂Zr₂TiFeNbO₁₈ (termed as BPZTFNO) was synthesized by a solid-state method. The structural analysis as obtained from the X-ray pattern has depicted an orthorhombic phase. The various size and morphology of grains are distributed throughout the natural surface as revealed from microstructure analysis. The dielectric and electrical study of the BPZTFNO is taken at a various sweep of frequency (1 kHz–1 MHz) and temperatures (25–400 °C). The ferroelectric-paraelectric phase transition is well illustrated from the temperature-dependent dielectric constant. The complex impedance analysis suggests the association of grain effect. The relaxation of non-Debye nature is shown in the impedance study. The formed sample is subjected to an electric field and further its excitation performance is examined suggesting its possible usage in devices.     

以四个参数为主线讲授高分子电学性质

高分子的电学性质物理概念抽象、数理内容多,初学者难以掌握要领。不少学生学完课程后仍不清楚表征高分子的电学性质需要哪些参数,在选择特定应用的高分子材料时不知采用何种参数为判据。本文结合作者的教学实践,提出将介电常数、介电损耗、介电强度以及电导率等四个参数作为教学主线,明确学习目标,以提高教学效果。文中针对一些难教和难学的内容介绍了作者的教学体会,重点介绍了介电常数的物理意义和介电损耗的起源,希望有利于相关老师的教学。     

Thermal and dielectric properties of PEO/EC/Pr4N+I− polymer electrolytes for possible applications in photo-electro chemical solar cells

The anion-conducting polymer electrolyte polyethylene oxide (PEO)/ethylene carbonate (EC)/Pr₄N⁺I⁻/I₂ is a candidate material for fabricating photo-electrochemical (PEC) solar cells. Relatively high ionic conductivity values are obtained for the plasticized electrolytes; at room temperature, the conductivity increases from 7.6 × 10⁻⁹ to 9.5 × 10⁻⁵ S cm⁻¹ when the amount of EC plasticizer increases from 0% to 50% by weight. An abrupt conductivity enhancement occurs at the melting of the polymer; above the melting temperature, the conductivity can reach values of the order of 10⁻³ S cm⁻¹. The melting temperature decreases from 66.1 to 45.1 °C when the EC mass fraction is increased from 0% to 50%, and there is a corresponding reduction in the glass transition temperature from −57.6 to −70.9 °C with the incorporation of the plasticizer. The static dielectric constant values, , increase with the mass fraction of plasticizer, from 3.3 for the unplasticized sample to 17.5 for the 50% EC sample. The dielectric results show only small traces of ion-pair relaxations, indicating that the amount of ion association is low. Thus, the iodide ion is well dissociated, and despite its large size and relatively low concentration in these samples, the iodide ion to ether oxygen ratio is 1:68, a relatively efficient charge carrier. A further enhancement of the ionic conductivity, especially at lower temperatures, is however desired for these applications.     

Conductivity measurement and dielectric,impedance and modulus spectroscopic studies on bis (P-nitrophenol) melaminium monohydrate

The present work is aimed to study the dielectric and electrical characteristics of bis (P-nitrophenol) melaminium monohydrate (BNPM) over the temperature and frequency ranges of 333–453 K and 50 Hz–5 MHz, respectively. The dielectric properties such as dielectric constant (ε′), dielectric loss (ε″), ac-conductivity (σ_ac), real (M′) and imaginary part (M″) of dielectric modulus were investigated as a function of temperature and frequency. The impedance analysis has been carried out using Cole-Cole plots to elucidate the electrical conduction mechanism. Further, observations indicated that the grain boundaries are more resistive and capacitive than the grains, inducing inhomogeneity in the material, which, in turn, causes broad frequency-dependent dielectric anomalies. The observed frequency-dependence of the AC conductivity validated the Jonscher power law. Further, an asymmetric dispersion peak in the imaginary part of the electrical modulus (M”) was noticed, indicating that the fabricated material exhibits non-Debye relaxation behavior.     

Apparent giant dielectric constants, dielectric relaxation, and ac-conductivity of hexagonal perovskites La1.2Sr2.7BO7.33 (B=Ru, Ir)

We present a thorough dielectric investigation of the hexagonal perovskites La_1.2Sr_2.7IrO_7.33 and La_1.2Sr_2.7RuO_7.33 in a broad frequency and temperature range, supplemented by additional infrared measurements. The occurrence of giant dielectric constants up to 10⁵ is revealed to be due to electrode polarization. Aside of dc and ac conductivity contributions, we detect two intrinsic relaxation processes that can be ascribed to ionic hopping between different off-center positions. In both materials we find evidence for charge transport via hopping of localized charge carriers. In the infrared region, three phonon bands are detected, followed by several electronic excitations. In addition, these materials provide further examples for the occurrence of a superlinear power law in the broadband ac conductivity, which recently was proposed to be a universal feature of all disordered matter.     

Low-temperature impedance and dielectric relaxation of NiO nanocrystals

Low-temperatures impedance and dielectric properties of NiO nanocrystals as a function of particle size were investigated by alternative current impedance spectra. It is found that NiO nanocrystals showed distinct bulk and grain boundary conductions at low temperatures, which were almost the same within the experimental error during the decreasing and the subsequent increasing temperature processes. This result indicated that no further protons are formed during these temperature cycles. The conductivities are also highly dependent on the particle size. As the particle size reduced, the conductivities of NiO nanocrystals increased to show a maximum. Further particle size reduction less than 8.9 nm led to a sudden decrease in conductivity. The corresponding activation energies showed a minimum with varying the particle size. These observations were most likely due to the balance between the concentration of charge carriers, holes and protons.     

Study of the Effect of Temperature and Magnetic Field Variation on Dielectric Properties of Organic Liquids Using a Microwave Cavity Spectrometer

Abstract

The temperature and magnetic field variation have been studied for the dielectric properties of 2-chlorobutane, acetonitrile and nitrobenzene in their pure state using microwave cavity spectrometer at 9.0 GHz. The analysis of the observed data of width, shift and amplitude of resonance profile has been carried out by using Slater perturbation equations for the computation of relaxation time, activation energy and for the relative study of permittivity and dielectric loss. This work provides fruitful information about the macroscopic structure of the organic liquids chosen.     

The effect of gamma irradiation on electrical and dielectric properties of organic-based Schottky barrier diodes (SBDs) at room temperature

The effect of ⁶⁰Co (γ-ray) irradiation on the electrical and dielectric properties of Au/Polyvinyl Alcohol (Ni,Zn-doped)/n-Si Schottky barrier diodes (SBDs) has been investigated by using capacitance-voltage (C-V) and conductance-voltage (G/ω-V) measurements at room temperature and 1 MHz. The real capacitance and conductance values were obtained by eliminating series resistance (R_s) effect in the measured capacitance (C_m) and conductance (G_m) values through correction. The experimental values of the dielectric constant (ε′), dielectric loss (ε″), loss tangent (tanδ), ac electrical conductivity (σ_ac) and the real (M′) and imaginary (M″) parts of the electrical modulus were found to be strong functions of radiation and applied bias voltage, especially in the depletion and accumulation regions. In addition, the density distribution of interface states (N_ss) profile was obtained using the high-low frequency capacitance (C_HF-C_LF) method for before and after irradiation. The N_ss-V plots give two distinct peaks for both cases, namely before radiation and after radiation, and those peaks correspond to two different localized interface states regions at M/S interface. The changes in the dielectric properties in the depletion and accumulation regions stem especially from the restructuring and reordering of the charges at interface states and surface polarization whereas those in the accumulation region are caused by series resistance effect.     

Ferroelectric and dielectric properties of bismuth-layered structural Sr2Bi4−xLnxTi5O18 (Ln=La, Nd, Sm and Dy) ceramics

La, Nd, Sm, and Dy-doped Sr₂Bi₄Ti₅O₁₈ (SBTi) ceramic samples have been prepared by the solid-state reaction method. The X-ray diffraction reveals that all of the ceramic samples are single phase compounds. Their remnant polarization (2P_r) increases at first, and then decreases with the increase of doping content. When doping content is 0.01, Sm and Dy-doped SBTi samples exhibit the maximum 2P_r of 18.2 and 20.1 μC/cm², respectively. While La and Nd-doped SBTi samples display the maximum 2P_r value of 18.4 and 19.1 μC/cm² with doping content of 0.05 and 0.10, respectively. The ferroelectric properties of Sr₂Bi_4−xLn_xTi₅O₁₈ are found to be dominated by the competition of the decrease of oxygen vacancy concentration and the relief of structural distortion.     

(La0.4Ba0.4Ca0.2)(Mn0.4Ti0.6)O3: A new titano-manganate with a high dielectric constant and antiferromagnetic interactions

A new perovskite-based titano-manganate, (La_0.4Ba_0.4Ca_0.2)(Mn_0.4Ti_0.6)O₃, has been prepared by the ceramic route at 1100°C. This oxide was found to possess the cubic perovskite structure with  Å (space group ). The refined composition as obtained by Rietveld analysis of powder X-ray data was found to be (La_0.44Ba_0.38Ca_0.18)(Mn_0.43Ti_0.57)O_2.91(3) (R_p=0.0704, wR_p=0.0828). The composition was also ascertained by Energy dispersive X-ray analysis. Iodometric studies led to a slightly higher oxygen content (compared to Rietveld refinement) corresponding to an average manganese oxidation state of 3.05. The above oxide was found to exhibit high dielectric constant (ε) of 6980 at 1 kHz decreasing to 590 at 100 kHz. At high temperatures (200°C) it shows an unusually high dielectric constant of 20,000 at 1 kHz. In addition to the dielectric properties, detailed magnetic studies show evidence of long-range antiferromagnetic interactions near 5 K. The presence of unusually high dielectric constant coupled with the long-range magnetic interactions may open up interesting applications.     

原位聚合法制备聚吡咯-钴铜锌铁氧体复合材料及其电磁性能

采用自蔓延燃烧法和原位聚合法分别制备纳米Co0.7Cu0.1Zn0.2Fe2O4铁氧体和聚吡咯(PPy)-Co0.7Cu0.1Zn0.2Fe2O4纳米复合材料.采用X射线衍射仪(XRD)、透射电子显微镜(TEM)和傅里叶红外光谱(FTIR)对材料的结构和形貌进行表征,使用波导法和振动样品磁强计(VSM)研究了材料的介电性能、微波吸收性能和磁性能.结果表明,制得了纯相的尖晶石结构Co0.7Cu0.1Zn0.2Fe2O4铁氧体,少量Cu2+离子替代了铁氧体八面体位置上的Co2+离子,使得材料的晶格常数减小;2种粉体粒子分散性较好,它们的平均粒径分别约为15 nm和50 nm;在5.0~20.0 GHz频率范围内,PPy-Co0.7Cu0.1Zn0.2Fe2O4复合材料的反射损耗在-16.25 dB到-20.27 dB之间,且在18 GHz处出现极大值-20.27 dB, 带宽为2.0 GHz(最强峰的半高宽),PPy-Co0.7Cu0.1-Zn0.2Fe2O4复合材料的反射损耗明显大于铁氧体; PPy-Co0.7Cu0.1Zn0.2Fe2O4的饱和磁化强度(Ms)和剩余磁化强度(Mr)分别为12.9 A/g和4.29 A/g,小于Co0.7Cu0.1Zn0.2Fe2O4铁氧体的相应值,但复合材料的矫顽力大于Co0.7Cu0.1Zn0.2Fe2O4铁氧体的,为38.96 kA/m.     

The thermal and dielectric properties of high performance cyanate ester resins/microcapsules composites

Novel high performance bisphenol A dicyanate ester (BADCy) resins/poly(urea-formaldehyde) microcapsules filled with epoxy resins (MCEs) composites have been prepared. The effects of different contents of MCEs on the thermal and dielectric properties of cured BADCy were investigated using dynamic mechanical analyzer (DMA), thermalgravimetric analyzer (TGA) and broadband dielectric analyzer. The dielectric properties of BADCy/MCEs treated in hot water and hot air were also discussed. The morphologies of BADCy/MCEs composites were characterized by scanning electron microscopy (SEM). Results indicate that the appropriate content of MCEs can improve or maintain the thermal stability, the low dielectric constant and dielectric loss of cured BADCy mainly owing to higher conversion of cyanate ester (-OCN) groups. After aged in hot water and hot air, respectively, BADCy/MCEs composites with small content of MCEs can retain the low dielectric constant and dielectric loss.