高介电常数、低介电损耗的聚合物基复合材料*

考虑到高介电常数、低介电损耗聚合物基复合材料在电气、电子行业的广泛重要应用,本文对其研究进展进行了回顾。重点讨论了功能填料、聚合物基体及它们两者的相互作用等因素对聚合物基复合材料介电性能的影响规律,试图为建立高介电常数、低介电损耗的聚合物基复合材料的设计和制备原理理清思路。指出该领域在未来的主要发展方向是涉及制备结构、形貌、尺寸可控的新的功能填料,探索新型简单的复合工艺和界面控制技术,从理论上分析建立功能填料的结构和介电性能的关系模型等。     

An Electric Criterion to Evaluate Glass Transition Temperature: Dielectric Relaxation Measurements

In this contribution, a dielectric measurement technique for the evaluation of phase transition temperature and the study of physical aging on polymeric thin films is considered. This kind of measurement provides the possibility of displaying phase transitions with a high degree of precision. Furthermore, it can be considered alternatively to techniques not applicable in the case of thin films, such as Differential Scanning Calorimetry (DSC). In this work, owing to the high sensitivity of the utilized experimental set-up, a glass transition T_G of 156 K, with a precision equal to 0.3%, and a melting T_M = 220 K have been assessed for 4 µm thick Polydimethylsiloxane (PDMS) films. Performing measurement as a function of time, it was possible to monitor physical aging phenomena, mainly consisting in a change of dielectric properties. As expected, the time evolution of the aging phenomena can be described by a simple logarithmic law.     

NMR仪器温控系统测试与校正

介绍了一型自主研制的温控系统的原理与结构,采用核磁共振(NMR)实验测温方法检测了温控系统的精确性和稳定性.针对精确性进行了设计校正,校正后精确度达到了±0.2℃.指出了稳定性方面的特点与不足之处,提出改进意见.     

Dielectric relaxation of polystyrene with side-chain- and chain-end-labels

Polystyrenes with different concentrations of side groups with cyano groups were prepared and complex dielectric constants were measured in the range of the glass transition temperature and the frequency range of 10^–2–10⁷ Hz.The GPC and DSC measurements showed that the molecular weight of these polystyrenes was about 10500 g/mole and the glass transition temperatures were 89.5°C for all samples.The dielectric relaxation spectra obtained for the side group polystyrene labels and also the chain-end polystyrene labels prepared before [9] were analyzed to find out the degree of coupling of the chain-end and side-group labels with the cooperative reorientation of the polymeric matrix. The analysis of the spectra was carried out using the analysis method developed by Mansour and Stoll [6].The results obtained showed that both end- and side-group labels are strongly coupled with the segmental reorientation and relax with relaxation times longer than that of the segments.The value of logf _m = (logf _m(label)) – logf _m(matrix)) was obtained from the recently designed comparison diagram suggested by Mansour and Stoll [6, 14]. The value of logf _m depends on the label length in the case of chain-end labels.It was surprising to find that the side groups relax slower than the segments by only 0.9 decades. These results obtained implied that the label relaxes through a multistep relaxation mechanism of the side and end groups and not through a diffusion mechanism of the whole chain. In addition, the effective lengths of the relaxing units were determined using the empirical equation obtained before in the case of rodlike molecules in polyisoprene [7].     

Broadband Dielectric Relaxation Spectroscopy in Polymer Nanocomposites

Summary: Dielectric spectroscopy in the frequency domain and thermally stimulated depolarization currents techniques, covering together a broad frequency range (10⁻⁴–10⁹ Hz), were employed to investigate molecular dynamics in relation to structure and morphology in polymeric nanocomposites. Several systems were investigated, three of them with the same epoxy resin matrix and different inclusions (modified smectite clay, conducting carbon nanoparticles and diamond nanoparticles) and two with silica nanofiller (styrene-butadiene rubber/silica and polyimide/silica nanocomposites). Special attention was paid to the investigation of segmental dynamics associated with the glass transition of the polymer matrix, in combination also with differential scanning calorimetry measurements. Effects of nanoparticles on local (secondary) relaxations and on the overall dielectric behavior were, however, also investigated. Several interesting results were obtained and discussed for each of the particular systems. Two opposite effects seem to be common to the nanocomposites studied and dominate their behavior: (1) immobilization/reduction of mobility of a fraction of the chains at the interface to the inorganic nanoparticles, due to chemical or physical bonds with the particles, and (2) loosened molecular packing of the chains, due to tethering and geometrical confinement, resulting in an increase of free volume and of molecular mobility.     

Advances in Dielectric Elastomers for Actuators and Artificial Muscles

A number of materials have been explored for their use as artificial muscles. Among these, dielectric elastomers (DEs) appear to provide the best combination of properties for true muscle‐like actuation. DEs behave as compliant capacitors, expanding in area and shrinking in thickness when a voltage is applied. Materials combining very high energy densities, strains, and efficiencies have been known for some time. To date, however, the widespread adoption of DEs has been hindered by premature breakdown and the requirement for high voltages and bulky support frames. Recent advances seem poised to remove these restrictions and allow for the production of highly reliable, high‐performance transducers for artificial muscle applications.

     

Crystallization of Polymers Studied by Temperature Modulated Calorimetric Measurements at Different Frequencies

Quasi-isothermal temperature modulated DSC (TMDSC) were performed during crystallization to determine heat capacity as function of time and frequency. Non-reversible and reversible phenomena in the crystallization region of polymers were distinguished. TMDSC yields new information about the dynamics of local processes at the surface of polymer crystals, like reversible melting. The fraction of material involved in reversible melting, which is established during main crystallization, keeps constant during secondary crystallization for polycaprolactone (PCL). This shows that also after long crystallization times the surfaces of the individual crystallites are in equilibrium with the surrounding melt. Simply speaking, polymer crystals are living crystals. A strong frequency dependence of complex heat capacity can be observed during and after crystallization of polymers.This revised version was published online in November 2005 with corrections to the Cover Date.     

储能薄膜电容器介电高分子材料

高功率密度、高充放电效率以及超长使用寿命等特点是聚合物薄膜电容器能够广泛应用于电动汽车、智能电网等各类电子电气领域中的重要原因。其中,介电高分子材料因其质轻、击穿强度高、易大规模加工等优点赋予了薄膜电容器更多的可能性。但同时,介电高分子的介电常数普遍较低,导致所制备的电容器能量密度偏低因而不能更好地适应设备小型化轻型化的要求。本文概述了电介质以及薄膜电容器的基本原理以及性能参数,着重介绍了以储能为主要研究方向的介电高分子材料,主要包括聚合物基纳米复合介电高分子、偶极玻璃聚合物、交联型介电高分子以及多组分全有机介电高分子。最后对介电高分子在制备性能优异的储能电容器过程中面临的多重挑战和潜在机遇进行了总结。     

Temperature Calibration of TMAs Using Modulated Temperature and Curie Temperature Reference Standards

This article presents the concept of calibrating temperature in thermomechanical analyzers (TMA) using reference standard magnetic materials whose Curie temperatures are well-known. This concept has not been tested experimentally to the best of the author's knowledge. Electrical current applied to a unifilarly wound furnace results in the furnace acting as an electrical inductor. A magnetic material sample located within such a furnace practically constitutes a solenoid core. A modulated temperature program directly results in a corresponding varying force exerted by the sample against the TMA probe, if the probe's axis and the central induced magnetic field line of force are coaxial, and, furthermore, if the direction of the central magnetic field line of force and the expansion direction of the probe are identical. If a sample undergoes a Curie transition, then the force which the sample exerts against the probe will diminish to zero as the transition goes to completion. Using a modulated temperature program throughout this phase transition allows determination of transition completion, by observation of the point at which the force required to maintain the sample's physical position reaches a steady state from it's previously non-steady state. This revised version was published online in August 2006 with corrections to the Cover Date.     

Dipolar motions and phase transitions in a side‐chain polysiloxane liquid crystal. A study by thermally stimulated depolarization currents

The relaxation mechanisms present in a side‐chain liquid crystalline polymer have been studied by Thermally Stimulated Depolarization Currents (t.s.d.c.), in a wide temperature range covering the glassy state, the glass transition region, and the liquid crystalline phase. The thermal sampling procedure was used to decompose the complex relaxations into its narrowly distributed components. Three relaxation mechanisms were observed in this polymer: a relaxation below the glass transition temperature that is broad and extends from −150°C up to −110°C, the glass transition relaxation whose maximum intensity appears at ∼20°C, and a relaxation above the glass transition temperature, in the liquid crystalline phase. The attribution of these relaxations at the molecular level is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 227–235, 1999     

Magnetic Temperature Standards for TG

Magnetic transition temperatures, Tc, are measured by simultaneous TM/DTA for Alumel, cobalt, nickel, and three alloys of Ni and Co. The observed values of Tc are corrected using the values for the melting temperatures of pure metals used to define the International Temperature Scale. These corrections are based on the simultaneous melting of these pure metals alongside, but separate from, the magnetic sample. Nine investigators, using a wide variety of instrumentation, have made these measurements utilizing a standard protocol. The results are compared for several heating rates. It is planned to make these same magnetic materials ultimately available to the public for calibration of temperature of their TG instruments. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dielectric spectroscopy of nanocomposites based on iPP and aPS treated in the water solutions of alkali metal salts

In this paper, a new simple and environmentally friendly treatment technique for obtaining polymer nanocomposites with appropriate dielectric properties has been presented. Sheets of isotactic polypropylene and atactic polystyrene were immersed in 3 saturated water solutions of alkali metal salts (LiCl, NaCl, and KCl) at 2 fixed temperatures (23°C and 90°C), and 3 DC electrical potentials (+4 kV, −4 kV, and ground potential) were applied. A quantification of alkali metals in the polymer sheets was conducted by inductively coupled plasma optic emission spectrometry. The obtained concentration values were from 7.38·10⁻⁹ mol/cm³ to 1.25·10⁻⁷ mol/cm³. The qualitative analysis of potassium distribution in the polymer matrix was conducted by time‐of‐flight secondary ion mass spectrometry cross‐sectional record. The relative dielectric constant (ε′) of samples was investigated in the frequency range from 20 Hz to 9 MHz at the constant temperature of 22°C. Stable values of ε′ in fully measured frequency range were observed for both pure and treated samples. Next, the results of the dielectric spectroscopy measurements were compared and established the kind of treatment that provided the highest value of ε′. The relationship between the concentrations of alkali metals and the values of relative dielectric constant was determined for the samples obtained by a treatment at 90°C and +4 kV.     

低温固态反应制备纳米Ba_(1-y)Sr_yTi_(1-x)Zr_xO_3介电材料及性能研究

将TiCl4的水解产物与固体Ba(OH)2按摩尔比1∶1混合,混合物经室温研磨、100℃烘干,得到钛酸钡纳米晶;按相同工艺掺杂,合成了一系列Ba1-ySryTi1-xZrxO3(0x≤0.3,0y≤0.4)固溶体;采用X射线衍射分析了产物的晶体结构,采用透射电镜观察了其形貌;并测定了系列固溶体的室温介电常数、介电损失.结果表明,所制备的Ba1-ySryTi1-xZrxO3为完全互溶取代固溶体,由平均粒径70 nm的球形微粒组成.经低温固态反应掺入适量锆、锶后,BaTi O3的室温介电常数由3 000提高到20 000左右.     

Dielectric relaxation and ionic transport in poly(ethylene carbonate)‐based electrolytes

To study the ion‐conductive and dielectric properties of polymer electrolytes based on poly(ethylene carbonate) (PEC) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), the complex permittivity and conductivity were measured using broadband dielectric spectroscopy. The temperature dependence of the relaxation frequency and ionic conductivity for PEC‐LiTFSI electrolytes (1 – 200 mol%) indicates that the segmental motion of PEC chains decreases with the addition of just 1 mol% of Li salt and increases with increasing concentration above 10 mol%. According to the Walden rule for PEC‐based electrolytes, the value of deviation from the reference line increased, and the fragility and decoupling exponents decreased with increasing salt concentration. These results indicate that there are large numbers of ion pairs and aggregated ions, which imply low ionicity and reduced fragility in highly concentrated PEC‐based electrolytes. Copyright © 2016 John Wiley & Sons, Ltd.     

Dielectric relaxation spectroscopy and alignment behavior of a polymer‐dispersed liquid crystal and its component materials

The dielectric properties of a polymer‐dispersed liquid crystal (PDLC), a liquid‐crystal (LC) mixture (BL036), and three polymer matrices of PN314 containing different amounts of BLO36 were determined over a range of frequencies and temperatures and, for the LC and PDLC, over a range of voltages leading to homeotropic alignment of the LC. The overall dielectric relaxation process was a weighted sum of contributions from (1) the primary (δ) process in the LC arising from the motions of the dipoles about the short molecular axis and (2) dipole motions in the polymer matrix. The dielectric spectra were determined as a function of frequency, temperature, and, when appropriate, applied voltage. An equivalent electrical circuit was used as a working model to describe the dielectric behavior of the PDLC in the absence and presence of applied voltages. Agreement between the dielectric data and this model was achieved if a portion of the LC phase at the interface was assumed to be immobile. The director order parameter for the LC component in the PDLC was determined from dielectric measurements as the material was aligned homeotropically in an applied electric field. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1173–1194, 2001     

Thermally Stimulated Current Spectroscopy of Amorphous and Semi-Crystalline Polymers

Thermally Stimulated Current (TSC) spectrometry has been applied to the characterization of polymeric materials. The study of a series of amorphous polymers having different physical structures has shown that the compensation parameters are independent of physical aging; contrarily, the activation enthalpy distribution reflects the evolution of the heterogeneity of the amorphous phase. In copolymers, TSC allows us to identify segregated amorphous phases. In semi-crystalline polymers, with semi-rigid chains, we have shown the existence of an amorphous crystalline interphase characterized by a plateau in the temperature distribution of activation enthalpy. This revised version was published online in August 2006 with corrections to the Cover Date.     

Temperature Dependence of the Dielectric Permittivity of Acetic Acid,Propionic Acid and Their Methyl Esters: A Molecular Dynamics Simulation Study

For most liquids, the static relative dielectric permittivity is a decreasing function of temperature, because enhanced thermal motion reduces the ability of the molecular dipoles to orient under the effect of an external electric field. Monocarboxylic fatty acids ranging from acetic to octanoic acid represent an exception to this general rule. Close to room temperature, their dielectric permittivity increases slightly with increasing temperature. Herein, the causes for this anomaly are investigated based on molecular dynamics simulations of acetic and propionic acids at different temperatures in the interval 283–363 K, using the GROMOS 53A6_OXY force field. The corresponding methyl esters are also considered for comparison. The dielectric permittivity is calculated using either the box‐dipole fluctuation (BDF) or the external electric field (EEF) methods. The normal and anomalous temperature dependences of the permittivity for the esters and acids, respectively, are reproduced. Furthermore, in the EEF approach, the response of the acids to an applied field of increasing strength is found to present two successive linear regimes before reaching saturation. The low‐field permittivity ε, comparable to that obtained using the BDF approach, increases with increasing temperature. The higher‐field permittivity ε′ is slightly larger, and decreases with increasing temperature. Further analyses of the simulations in terms of radial distribution functions, hydrogen‐bonded structures, and diffusion properties suggest that increasing the temperature or the applied field strength both promote a relative population shift from cyclic (mainly dimeric) to extended (chain‐like) hydrogen‐bonded structures. The lower effective dipole moment associated with the former structures compared to the latter ones provides an explanation for the peculiar dielectric properties of the two acids compared to their methyl esters.     

非均匀体系介电研究的现状与展望*

用介电谱方法讨论化学中的非均匀体系是近十几年发展起来的交叉性新领域, 它在分散体系、高分子膜以及生物细胞体系的研究中占有重要地位。本文从理论和应用两方面综述该领域的发展过程及研究现状, 并结合实例阐述了构造和介电弛豫模式的关系以及该方法的特点。在对遗留问题和最新进展给予评述性讨论的同时, 指出了进一步的研究方向。