Influence of morphological and conformational changes on the molecular mobility in poly(ethylene naphthalene-2,6-dicarboxylate)

Dynamic electric (DEA) and mechanical (DMA) analyses were combined to explore the relaxational processes in amorphous and semicrystalline poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) samples. Differential scanning calorimetry measurements were carried out to investigate the crystallinity of the samples following isothermal annealing treatment at 443 K. The two secondary relaxations β and β*, the main α relaxation, as well as the ρ-relaxational process, were revealed by both electric and mechanical viscoelastic responses of the PEN samples. DMA results clearly identified the above T_α loss factor peak, ρ, as a probe of the cold crystallization. However, the association of both DMA and DEA investigations pointed out that electric and non-electric aspects might govern the ρ-process.     

Dielectric phenomena and electrical energy storage of poly(vinylidene fluoride) based high-k polymers

Since the discovery of relaxor ferroelectric behavior was firstly reported in irradiated poly(vinylidene fluoridetrifluoroethylene) (P(VDF-TrFE)) copolymer, many strategies have been developed to enhance the electrical energy storage capability, including copolymerization, grafting, blending and fabricating of multilayer. This review article mainly summarizes the recent progresses on these strategies and aims to motivate the development of novel PVDF-based polymers for electrical energy storage and dielectric applications.     

Preparation of high quality electrical insulator self-assembled monolayers on gold. Experimental investigation of the conduction mechanism through organic thin films

Self-assembled monolayers (SAMs) form highly ordered, stable dielectrics on conductive surfaces. Being able to attach larger-area contacts in a MIM (metal-insulator-metal) diode, their electrical properties can be determined. In this paper, the electrical conduction through thiolate SAMs of different alkyl chain lengths formed on gold surfaces were studied and discussed. The influence of the headgroup with respect to the surface quality and prevention of short circuits is investigated. Phenoxy terminated alkanethiols were found to form high quality SAMs with perfect insulating properties. Synthesis of the required terminally substituted long chain thiols have been developed. The I(V) characteristics of MIM structures formed with these SAMs are measured and simulated according to theoretical tunneling models for electrical conductivity through thin organic layers. SAM based electronic devices will become especially important for future nanoscale applications, where they can serve as insulators, gate dielectric of FETs, resistors, and capacitor structures.     

Study on the relation of solvent extractable material and resistivity of pyrolysed coal

Changes in electrical and dielectric properties along with yield of the material extracted with pyridine and chloroform depending on the temperature of pyrolysis were analyzed for the two samples of coals with different ranks.The material soluble in pyridine but insoluble in chloroform and the material soluble in chloroform were investigated with Fourier transform infrared spectroscopy (FT-IR) method using attenuated total reflection techniques (ATR).It was stated that an anomalous course of the changes in resistivity of pyrolysates, which were separated from the zones of the charge being plasticized, was related with the existence of low molecular compounds in the supramolecular structure of pyrolysates. These low molecular compounds functionate as dielectrics and block the transport of electric charge in the carbon matrix.     

Synthesis,physical characterization,and acetone sorption kinetics in random copolymers of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalate)

Random copolymers of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN) were synthesized by melt condensation. In a series of thin, solvent cast films of varying PEN content, acetone diffusivity and solubility were determined at 35°C and an acetone pressure of 5.4 cm Hg. The kinetics of acetone sorption in the copolymer films are well described by a Fickian model. Both solubility and diffusivity decrease with increasing PEN content. The acetone diffusion coefficient decreases 93% from PET to PET/85PEN, a copolymer in which 85 weight percent of the dimethyl terephthalate in PET has been replace by dimethyl naphthalate 2,6-dicarboxylate. The acetone solubility coefficient in the amorphous regions of the polymer decreases by approximately a factor of two over the same composition range. The glass/rubber transition temperatures of these materials rise monotonically with increasing PEN content. Copolymers containing 20 to 80 wt % PEN are amorphous. Samples with <20% or >80% PEN contain measurable levels of crystallinity. Estimated fractional free volume in the amorphous regions of these samples is lower in the copolymers than in either of the homopolymers. Relative free volume as probed by positron annihilation lifetime spectroscopy (PALS) decreases systematically with increasing PEN content. Acetone diffusion coefficients correlate well with PALS results. Infrared spectroscopy suggests an increase in the fraction of ethylene glycol units in the trans conformation in the amorphous phase as the concentration of PEN in the copolymer increases. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2981–3000, 1998     

Dielectric and conductivity processes in poly(ethylene terephthalate) and poly(ethylene naphthalate) homopolymers and copolymers

Electrical relaxation and conductivity processes in amorphous and semicrystalline poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) homopolymers and certain PET/PEN copolymers have been studied by means of dielectric spectroscopy. Homopolymers and copolymers able to crystallize were subjected to successive thermal runs to investigate the influence of the thermal history upon the morphology and the electrical behavior of the polymeric systems. The morphology of the untreated as well as the heat‐treated specimens was determined by means of Differential Scanning Calorimetry (DSC). All samples exhibit β‐relaxation process, due to local motions of the C?O polar side groups, and α‐relaxation process associated to the glass/rubber transition. In the PEN spectrum an additional, subglass, mode was recorded, most probably attributed to cooperative motions of the naphthalene groups. Finally, the dynamic nature of the crystallization process is expressed via the over glass transition mode and the temperature dependence of dc conductivity recorded in amorphous PET, PEN, and PET/PEN (85/15) (wt/wt) samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3078–3092, 2006     

Electro- and Photoconductivity of Polymer Films Based on 7-Octen-2,4-dionatocobalt

The characteristics of the dark current and photocurrent of samples with sandwich structures with films of macromolecular chelates based on 7-octen-2,4-dionatocobalt. The electro- and photoconductivities increase somewhat with an increase in temperature over the 290-370 K range with small electrical field intensity, but they decrease in large electric fields. A change in the nature of the conductivity from semiconductor to metallic was observed with increase in electric field. It is proposed that the number of cobalt ions, through which electron transfer occurs, changes with changes in the electrical field or the temperature.     

Enhanced electrostriction based on plasticized relaxor ferroelectric P(VDF‐TrFE‐CFE/CTFE) blends

The purpose of this work aims at enhancing the electrostrictive strain response and the mechanical energy density under moderate electric field, which is essential for actuator applications. For achieving this, plasticized effects as well as the influence of chlorofluoroethylene and chlorotrifluoroethylene defects on the electromechanical behavior of the copolymer matrix poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) are investigated. Experimental results showed that the plasticized terpolymer‐based CFE presented better electrical and mechanical performances than the CTFE one. Furthermore, such interesting properties exhibited superior advantages when CFE was combined with (DEHP) plasticizer, resulting in excellent electrostrictive strain response as well as mechanical energy density. Another aspect of this work reports on the influence of the composition, especially the CTFE content, on the electromechanical properties of the neat and plasticized P(VDF‐TrFE‐CTFE). This enables the determination of the desired terpolymer compositions for given applications, which are based on different criteria, such as crystallinity, elastic modulus, dielectric permittivity, and so forth. All the results demonstrated a possibility to realize high performance electroactive polymer actuators while achieving significant improved strain response and energy density under relatively low electric field. Such an investigation allows overcoming the current technological barrier of conventional electroactive polymers that suffer from the high applied electric field usually required to reach sufficient strain. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1368–1379     

聚2,6-萘二甲酸乙二醇酯β松弛的热释电研究

本文用短路热释电方法研究了聚萘酯(PEN)的β松弛过程。极化场强和电极效应的实验结果表明,PEN的TSC图谱中50℃的β松弛过程是偶极松弛过程。并且此松弛峰电流值随样品结晶度的增加而降低。用“初始升高法”计算得到其松弛活化能约为0.34eV,且不受结晶度变化的影响。这些实验结果说明β松弛是非晶区小链段的局部运动。     

Percolation of carbon nanomaterials for high-k polymer nanocomposites

This review summarized the recent progress towards high-k polymer composites bases on the near-percolated networks of carbon nanomaterials by focusing on the effects of distinct network morphologies on the dielectric properties. It is expected to give guidance on designing new near-percolated networks in polymer matrices towards next-generation polymer dielectrics.     

Some electrical properties of wood pulp treated with sodium hydroxide

The effect of the degree of crystallinity and degree of polymerization on the electrical properties of soda-treated wood pulp has been investigated. The dielectric constant (E′) and the dielectric loss (E″) were measured for the treated samples over a frequency band 0.2–10 MHz at 20°C. Also, the electrical conductivity (σ) was calculated from the measured data of the dielectric constant. From the results obtained we found that the degree of crystallinity and the degree of polymerization decrease with time of oxidation while the number of carboxylic groups increased. E″,E′, and σ were found to increase with the decrease in the degree of crystallinity.     

Water sorption/desorption kinetics in poly(ethylene naphthalene-2,6-dicarboxylate) and poly(ethylene terephthalate)

Water sorption/desorption experiments were carried out on films (～ 220 μm thick) of amorphous poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) stored in ambient conditions for different periods of time (0.5-4 years) and of poly(ethylene terephthalate) (PET) with different degrees of crystalinity levels (0-29%) by means of FTIR spectroscopy. Water sorption/desorption kinetics follows Fick's law for all samples investigated. Water sorption isotherms, obtained from gravimetric methods, indicate a larger sorption capacity in the case of PEN materials. The apparent diffusion coefficients (D) are larger in the case of PET samples. The observed D values decrease with storage time (physical aging) of PEN samples and with the crystallinity of PET samples. © 1995 John Wiley & Sons, Inc.     

Autonomic self-healing lipid monolayer: a new class of ultrathin dielectric

The electrical performance of stabilized lipid monolayers on H-terminated silicon is reported for the first time. We show that these 2.7 nm thick only ultrathin layers present extremely low current leakage at high electric field and high breakdown voltage that both compare favorably with the best data reported on organic thin film dielectrics. We demonstrate a very unique property of autonomic self-healing of the layer at room temperature with the total recovery of its performance after electrical breakdown. The mechanisms involved in breakdown and self-healing are described.     

Improvement of electrical and material properties of epoxy resin/ aluminum nitride nanocomposites for packaging materials

This paper presents the influence of Aluminum Nitride (AlN) nanoparticles on the electrical and material properties of epoxy resin (EP). The EP/AlN nanocomposites with different concentrations of nano-AlN fillers are prepared. The dispersion of the nano-AlN particles in the composites is analyzed by a field emission scanning electron microscope (FESEM). The electrical properties are investigated by the space charge and DC conductivity measurements, whereas the material properties are studied by Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. The results show that the homo-charge accumulation appears near both electrodes during the polarization, but there are limited negative charges left near both electrodes in the depolarization for the pure EP sample. There is no space charge accumulation in the 1 wt% and 2 wt% EP/AlN nanocomposites. The electric field distortion of the pure EP sample is 20%. Moreover, the electric field distortion initially decreases with the increase of the nano-AlN content, but it increases for the 2 wt% nano-AlN sample. Temperature has a dominant influence on the DC conductivity of the EP/AlN nanocomposites comparing to the pure EP. However, the DC conductivity of the nanocomposites becomes stable at high temperatures. It is also found that the weight loss of the samples decreases with the addition of the nano-AlN and the 1 wt% nano-AlN sample has the highest glass transition temperature. It is elucidated that the high apparent mobility and activation energy facilitate the space charge transport and suppressing the space charge accumulation. Furthermore, the nano-AlN filler can increase the trap level and trap energy density of the deep traps in the sample. The dielectric loss of the EP at high frequency is reduced with the content of 1 wt% nano-AlN. Furthermore, the addition of the nano-AlN can improve the thermal stability of the EP. The 1 wt% nano-AlN sample has the superior electrical insulation and material performance amongst the tested materials.     

Processing optimization: A way to improve the ionic conductivity and dielectric loss of electroactive polymers

Electro‐active polymers (EAPs) such as P(VDF‐TrFE‐CTFE) are greatly promising in the field of flexible sensors and actuators, but their low dielectric strength driven by ionic conductivity is a main concern for achieving high electrostrictive performance. It is well known that there is a quadratic dependence of the strain response and mechanical energy density on the applied electric field. This dependence highlights the importance of improving the electrical breakdown EAPs while reducing the dielectric losses. This article demonstrates that it is possible to dramatically increase the electrical breakdown and decrease the dielectric losses by controlling processing parameters of the polymer synthesis and fabrication procedure. As a result, an enhancement of around 70% is achieved in both the strain and blocking force. The effects on the dielectric losses of the polymer crystallinity, molecular weight, solvent purity, and crystallization temperature are also investigated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1164–1173     

Effect of nitrogen plasma treatment on the crystallinity and self‐bonding of polyetheretherketone (PEEK) for biomedical applications

Polyetheretherketone (PEEK) is a thermoplastic material with outstanding properties and high potential for biomedical applications, including hermetic encapsulation of active implantable devices. Different biomedical grade PEEK films with initial degree of crystallinity ranging from 8% to 32% (with or without mineral filling) were inspected. PEEK surfaces were treated with nitrogen RF plasma and the effects on materials crystallinity and self‐bonding were evaluated. In particular, the relationship between auto‐adhesive properties and crystalline content of PEEK before and after plasma treatment was examined. PEEK samples showed different bonding strength depending on their degree of crystallinity, with higher self‐bonding performance of mineral‐filled semi‐crystalline films. XRD did not show any modification of the PEEK microstructure as a result of plasma treatment, excluding a significant influence of crystallinity on the self‐bonding mechanisms. Nevertheless, plasma surface treatment successfully improved the self‐bonding strength of all the PEEK films tested, with larger increase in the case of semi‐crystalline unfilled materials. This could be interpreted to the increase in chain mobility that led to interfacial interpenetration of the amorphous phase.     

Thermal and electrical properties of porphyrin derivatives and their relevance for molecule interferometry

The authors present new measurements of thermal and electrical properties for two porphyrin derivatives. They determine their sublimation enthalpy from the temperature dependence of the effusive beam intensity. The authors study H2TPP and Fe(TPP)Cl in matter-wave interferometry. Both molecules have nearly equal de Broglie wavelengths but different internal characteristics: only Fe(TPP)Cl exhibits an electric dipole moment of about 2.7 D and the authors discuss its influence on the molecular interference pattern. The authors add an external electric force field to the interferometer and use it to measure the scalar polarizability. They compare their experimental values alpha(H2TPP)=105+/-4+/-6 A3 and alpha(Fe(TPP)Cl)=102+/-9+/-6 A3 to ab initio calculations and they discuss the influence of thermal excitations on the polarizability.