Structure–property relationship of polyimides based on pyromellitic dianhydride and short‐chain aliphatic diamines for dielectric material applications

Most polyolefins that are used for dielectric materials exhibit a low dielectric constant and operating temperatures up to 70°C. Polyimides offer a means to a higher dielectric constant material by the introduction of a polar group in the polymer backbone and are thermally stable at temperatures exceeding 250°C. A common dianhydride, pyromellitic dianhydride (PMDA), is reacted with various short‐chain diamines to produce polymers with high imide density. Homopolymers and copolymers synthesized had dielectric constants ranging from 3.96 to 6.57. These materials exhibit a dielectric constant twice that of biaxially oriented polypropylene and therefore a twofold increase in capacitance as well as maintaining low dissipation factors that are acceptable for this application. The experimental dielectric constants of these materials are also compared to density functional theory calculations and exhibit a close relationship. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1276‐1280, 2013     

Review of polymer materials with low dielectric constant

One of the exciting and promising developments in material science today is the design and synthesis of novel low‐dielectric‐constant polymer materials, which are found to have potential applications in the field of ultralarge‐scale integration, capacitors and other electronic circuits as insulating and/or dielectric materials. In this article the new polymer dielectric materials reported in recent years are reviewed, including aromatic (heteroaromatic) polymers, silicon‐containing polymers, fluorinated polymers, porous polymers, etc. In summarizing the review, the development, potential applications and future directions of polymer materials with low dielectric constant are discussed. Copyright © 2010 Society of Chemical Industry     

Thermosensitive dielectric properties in polyamide–phenol hybrid compounds and their application to the temperature-sensing wire

Thermosensitive dielectric properteis in polyamide–phenol hybrid compounds have been studied. The polyamide–phenol hybrid compounds are constituted of p-hydroxybenzoate–formaldehyde condensation oligomer dispersed molecularly in nylon 12 and polyamide copolymer. These materials are less hygroscopic than nylon 12 which is the least hygroscopic among polyamide homopolymers. It will be because the phenol group coordinates to amide group as the less hygroscopic “pseudo-water” instead of water. One of these materials has also shown an intrinsic hydrophobic effect of hydrogen bond segment due to the “hybrid effect” between polyamide and phenol. The thermosensitive dielectric properties are based on the temperature dependence of intermolecular hydrogen bond behaviors by amide and phenol groups, which have been discussed in relation with the molecular behaviors. The relationship with polarizations constituting dielectric constant and hydrogen bonding molecular segments, and ac hopping conduction behaviors by proton carriers have also been discussed. These materials are applied as a temperature-sensing material in a flexible thermosensing heater wire, which has three functions, that is, thermosensing, heating, and fusing for safe in the case of an abnormal overheat. As the features for a sensing material, these materials show the humidity low-dependence and highly thermal stability, and will be situated as one of the high-performance sensing material useful for the electric warmer such as an electric blanket.     

Epoxy polymers. V. Dielectric strength

This report deals with material properties which determine dielectric strength rather than phenomena that occur during breakdown. We propose that the determining factors are the same for liquids and polymers. We report dielectric strengths calculated from measured breakdown potentials and sample thicknesses for liquids, ionic solutions, and epoxy polymers doped with ionizable materials. The breakdown field (in liquids and polymers) is hypothesized to be that which generates some critical current density value in the dielectric. The reasons for this value being critical and characteristic of the material are unknown; however, the ionic current density that the measured breakdown field produces can be calculated from the Onsager theory of high-field electrolytic conduction, and this ionic current density is assumed to be the critical threshold quantity involved. Because of field effects on the dissociative ionization and conductivity of electrolytes in organic systems, the breakdown field varies with concentration and solute species, but the ionic current density associated with the breakdown field is essentially constant for a wide range of species and molar concentrations in a given solvent.     

Three dimensional solid-state supercapacitors from aligned single-walled carbon nanotube array templates

We demonstrate the fabrication of solid-state dielectric energy storage materials from self-assembled, aligned single-walled carbon nanotube arrays (VA-SWNTs). The arrays are transferred as intact structures to a conductive substrate and the nanotubes are conformally coated with a thin metal-oxide dielectric and a conductive counter-electrode layer using atomic layer deposition. Experimental results yield values in agreement with those obtained through capacitive modeling using Al₂O₃ dielectric coatings (C > 20 mF/cm³), and the solid-state dielectric architecture enables the operation of these devices at substantially higher frequencies than conventional electrolyte-based capacitor designs. Furthermore, modeling of supercapacitor architectures utilizing other dielectric layers suggests the ability to achieve energy densities above 10 W h/kg while still exhibiting power densities comparable to conventional solid-state capacitor devices. This device design efficiently converts the high surface area available in the conductive VA-SWNT electrode to space for energy storage while boasting a robust solid-state material framework that is versatile for use in a range of conditions not practical with current energy storage technology.     

Influence of the viscosity of poly(methyl methacrylate) on the cellular structure of nanocellular materials

Three different grades of poly(methyl methacrylate) (PMMA) with different rheological properties are used for the production of nanocellular materials using gas dissolution foaming. The influences of both the viscosity of the different polymers and the processing parameters on the final cellular structure are studied using a wide range of saturation and foaming conditions. Foaming conditions affect similarly all cellular materials. It is found that an increase of the foaming temperature results in less dense nanocellular materials, with higher cell nucleation densities. In addition, it is demonstrated that a lower viscosity leads to cellular polymers with a lower relative density but larger cell sizes and smaller cell nucleation densities, these differences being more noticeable for the conditions in which low solubilities are reached. It is possible to produce nanocellular materials with relative densities of 0.24 combined with cell sizes of 75 nm and cell nucleation densities of 10¹⁵ nuclei cm^?3 using the PMMA with the lowest viscosity. In contrast, minimum cell sizes of around 14 nm and maximum cell nucleation densities of 3.5 × 10¹⁶ nuclei cm^?3 with relative densities of 0.4 are obtained with the most viscous one. © 2019 Society of Chemical Industry     

Energy Storage in Ceramic Dielectrics

Historically, multilayer ceramic capacitors (MLC's) have not been considered for energy storage applications for two primary reasons. First, physically large ceramic capacitors were very expensive and, second, total energy density obtainable was not nearly so high as in electrolytic capacitor types. More recently, the fabrication technology for MLC's has improved significantly, permitting both significantly higher energy density and significantly lower costs. Simultaneously, in many applications, total energy storage has become smaller, and the secondary requirements of very low effective series resistance and effective series inductance (which, together, determine how efficiently the energy may be stored and recovered) have become more important. It is therefore desirable to reexamine energy storage in ceramics for contemporary commercial and near-commercial dielectrics. Stored energy is proportional to voltage squared only in the case of paraelectric insulators, because only they have capacitance that is independent of bias voltage. High dielectric constant materials, however, are ferroics (that is ferroelectric and/or antiferroelectric) and display significant variation of effective dielectric constant with bias voltage. The common ferroelectric materials, whether based upon barium titanate or lead manganese niobate (PMN), in the high-field limit, exhibit an energy storage which increases linearly with bias voltage. Mixed phase, ferroelectric plus antiferroelectric, dielectrics from the lead lanthanum zirconate titanate (PLZT) system, as predicted theoretically, show the best energy density at low to moderate fields. Surprisingly, maximum energy storage is not obtained in high dielectric constant materials but in those materials which display intermediate dielectric constant and the highest ultimate breakdown voltages.     

Metalphthalocyanines Anchored Poly(1,3,4-oxadiazole arylene ether)s: Optical and Electrical Studies

New phenolphthalein based poly(1,3,4-oxadiazole aryl ether) (PHOP) containing side chain carboxylic acid groups derived from 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole and 2-(bis(4-hydroxyphenyl)methyl)benzoic acid have been synthesized from typical aromatic nucleophilic substitution reaction. The PHOP seizes high dielectric constant (300 at 50 Hz) by the assistance of polar pendants and its findness in advance studies needs some structure modification with high dielectric constant metalphthalocyanine (MPc, M=Co, Ni & Cu) macrocycle to come out as further enhancement of dielectric constant and become photoactive polymer embedded metalphthalocyanine (PPEMP1–9). The molecular weight of PHOP was determined by gel permeation chromatography and is found to be 33375 (M _w/M _n = 2.48). All the tailor-made polymers were well characterized by Solid State UV–Vis, thermogravimetric analysis and XRD analysis. FTIR and NMR spectroscopic techniques confirms MPc units are grafted into the polymer matrix and act as a utmost light catching materials in the visible to near IR region (400–900 nm) with remarkable drop off in optical band gap and exhibited impressive thermal properties. The variation in the AC conductivity was explained by electron hopping model and values are in the range of 3.16 × 10^?5–4.78 × 10^?5 (S/m) at 5 MHz measured at 20 °C.     

Electrical properties of Cu(II) and Ni(II): N-salicylidene polymethacrylic acid hydrazide complexes

Different types of chelated polymer complexes have been synthesized to obtain improved electrical properties. Compact discs from powders of the chelated polymers were prepared and heated in a specially designed holder. Electrical conductivity and dielectric constant of Cu(II) and Ni(II): N-salicylidene polymethacrylic acid hydrazide samples were measured at a fixed frequency (1600 Hz) throughout the temperature range 25-150°C. The AC conductivity as well as dielectric measurements showed maxima at 85°C. The water molecules which were trapped in the polymer matrix are believed to play the main role in conduction and dielectric behaviour of the polymeric material. From the AC conductance and dielectric constant measurements, the dielectric losses of these polymeric materials were calculated as a function of temperature.     

Use of the dielectrometer for the determination of the complex dielectric constant in the microwave region in organic high polymers at various temperatures

A commercial type dielectrometer has been utilized for determining the complex dielectric constant of insulating materials as a function of temperature. For low-temperature measurements, modifications of the apparatus have been made, by which the lower section of the guide, containing the specimen, is insulated from the upper section by means of a Teflon disk, in order to permit measurements under vacuum without difficulties arising from moisture condensation. Taking into account the modifications made, relations between the experimentally measured quantities and the complex dielectric constant have been elaborated, and error analysis made, and best conditions to perform experimental measurements determined. For high- and medium-loss materials, in the low-temperature range, an accuracy of the order of 1% in ?′ and of 10% in ?″ have been calculated. Better results can be obtained for measurements at high temperature. The apparatus performance and the accuracy of measurements have been checked through measurements of the complex dielectric constant of different polar polymers at frequencies of the order of 9 × 10⁹ Hz, at temperatures between ?150 and 200°C. The experimental results are in good agreement with literature data derived from experimental measurements with other techniques and with the behavior expected on the basis of the results from radiofrequency measurements through considerations of molecular mobility in relation to molecular structure.     

A microcellular processing study of poly(ethylene terephthalate) in the amorphous and semicrystalline states. Part I: Microcell nucleation

Microcellular semicrystalline polymers such as poly(ethylene terephthalate) show great promise for engineering applications because of their unique properties, particularly at higher densities. Recent studies reveal some high density microcellular polymers have longer fatigue lives and/or equal strengths to the neat polymer. Relatively few microcellular processing studies of semicrystalline polymers have been presented. In general, semicrystalline polymers are relatively difficult to microcellular process compared to amorphous polymers. In this paper and a companion paper, the microcellular processing of poly(ethylene terephthalate) in the amorphous and semicrystalline states is studied in order to quantify the processing differences. The microcellular processing steps addressed in this paper include gas/polymer solution formation and microvoid nucleation. Particular emphasis is given to microvoid nucleation comparing the processing characteristics of semicrystalline and amorphous materials. Moreover, this study identifies a number of critical process parameters. In general, the semicrystalline materials exhibit ten to one thousand times higher cell nucleation densities compared with the amorphous materials, resulting from heterogeneous nucleation contributions. The amorphous materials show a strong dependence on cell density, while the semicrystalline materials show a weaker dependence. Moreover, classical nucleation theory is not adequate to quantitatively predict the effects of saturation pressure on cell nucleation for either the amorphous or semicrystalline polyesters. Both the semicrystalline and amorphous materials exhibit constant nucleation cell densities with increasing foaming time. Foaming temperatures near the glass transition are found to influence the cell density of the amorphous polyesters, indicating some degree of thermally activated nucleation. Furthermore, classical nucleation theory is not adequate to predict the cell density dependence on foaming temperature. Similar to the amorphous polyesters above the glass transition temperature, nucleation in the semicrystalline materials is found to be independent of the foaming temperature.     

Structural Analysis of silica aerogels for the interlayer dielectric in semiconductor devices

As semiconductor devices have become miniaturized and highly integrated, interconnection problems such as RC delays, power dissipation, and crosstalk appear. To alleviate these problems, materials with a low dielectric constant should be used for the interlayer dielectric in nanoscale semiconductor devices. Silica aerogel as a porous structure composed of silica and air can be used as the interlayer dielectric material to achieve a very low dielectric constant. However, the problem of its low stiffness needs to be resolved for the endurance required in planarization. The purpose of this study is to discover the geometric effect of the electrical and mechanical properties of silica aerogel. The effects of porosity, the distribution of pores, the number of pores on the dielectric constant, and elastic modulus were analyzed using FEM. The results suggest that the porosity of silica aerogel is the main parameter that determines the dielectric constant and it should be at least 0.76 to have a very low dielectric constant of 1.5. Additionally, while maintaining the porosity of 0.76, the silica aerogel needs to be designed in an ordered open pores structure (OOPS) containing 64 or more pores positioned in a simple cubic lattice point to endure in planarization, which requires an elastic modulus of 8 GPa to prevent delamination.     

Modelling the structural and physicomechanical properties of substituted poly(p-phenylene)s using molecular mechanical and molecular orbital methods

Conducting polymers are important technological materials that are finding increasing use in batteries and display devices. The conformation and packing of these polymers in the amorphous glassy state are poorly understood, despite the fact that they dictate their most important physical and mechanical properties. The processing of currently known conducting polymers is difficult and there is a strong incentive to increase their processability through functionalization. Developing an ability to predict the structure and structure-property relations of conducting polymers in the bulk will help with the design of new structures that combine processability with favourable electronic properties and facilitate their use in future high-technology applications. In this work, we concentrate on substituted poly(p-phenylene)s. Detailed atomistic molecular models have been developed with the help of molecular mechanics and semi-empirical quantum mechanical calculations using Cerius and MOPAC V6.0 program packages and structural, volumetric, and mechanical properties, e.g. geometrical values, densities, have been calculated by simulations on these models. The results from both methods have been compared with simulated and experimental data and conclusions have been drawn on the methodology and the approximations used. This study was used to compare with results obtained on unsubstituted poly(p-phenylene)s carried out earlier and to continue to develop our methodology for calculating structure, physical and mechanical properties that will be generally applicable to conductive polymers.     

Rational Design of Soluble Polyaramid for High‐Efficiency Energy Storage Dielectric Materials at Elevated Temperatures

High‐temperature polymer dielectrics are in great demand for harsh‐environment applications. Maintaining high‐energy storage density and low loss at elevated temperatures remains a major challenge for polymer dielectrics. In this work, a new type of polymer dielectric material is designed, which exhibits comparable dielectric properties in the start‐of‐the‐art dielectric nanocomposites and a superior potential for scale up. A soluble, glassy state polymer with a polarizing group is designed by introducing a weakly polar group into the polyaramid (PA) backbone to dilute the hydrogen bonding of the PA parent species. This increases the mobility of the molecular dipole within the polymer in the glassy state, thereby increasing its dielectric constant while maintaining the high‐temperature performance. The result of this design is a polymer with a glass transition temperature of 251 °C, a dielectric constant of up to 4.5, and a dielectric loss of 1%, while maintaining 2.1 J cm^?3 energy density and 86.8% efficiency at 200 °C. This polymer, with its excellent, intrinsic, electrical‐energy‐storage properties can also be adapted for a roll‐to‐roll capacitor film production. Breaking intermolecular hydrogen bonds to enhance the electrical‐energy‐storage properties of polymers is an excellent path for designing polymer dielectrics with high‐temperature capabilities.     

Chemical composition and temperature dependence of the energy storage properties of Ba1‐xSrxTiO3 ferroelectrics

Dielectric materials with high power and energy densities are desirable for potential applications in advanced pulsed capacitors. Computational material designs based on first‐principles calculations provide a “bottom‐up” method to design novel materials. Here, we present a first‐principles effective Hamiltonian simulation of perovskite ferroelectrics, Ba_1‐xSr_xTiO₃, for energy storage applications. The effects of different chemical compositions, temperatures, and external electric fields on the ferroelectric hysteresis and energy storage density of Ba_1‐xSr_xTiO₃ were investigated. The Curie temperature was tuned from 400 to 100 K by doping Sr in the BaTiO₃ lattice. At a constant temperature, the ferroelectric hysteresis became slimmer as the Sr content increased, and the energy storage efficiency increased. For the same chemical composition, the energy storage density increased as the temperature increased. For the composition x = 0.4, a discharged energy density of ~2.8 J/cm³ with a 95% efficiency was obtained in an external electric field of 350 kV/cm, and a discharged energy density of 30 J/cm³ with a 92% efficiency was obtained in an external electric field of 2750 kV/cm. The energy storage property predictions and new material designs have potential to create experimental and industrial products with higher energy storage densities.     

Structural,microwave permittivity,and complex impedance studies of cation (Cr,Bi, Al,In) substituted SrNi-X hexagonal nano-sized ferrites

Sr₂Ni₂T_xFe_28-xO₄₆ (T = Cr³⁺, Bi³⁺, Al³⁺, In³⁺; x = 0.25) hexa-ferrites were fabricated via the sol-gel route. The phase temperature, which was obtained using thermo-gravimetric analysis (TGA), reveals that the X-type hexagonal phase of these materials is highly stable above 1200 °C. The phase formation was confirmed using X-ray diffraction (XRD) patterns. The variation in lattice strain shows the significant effect of substituted cations on the structure of the materials. The crystallite size of these materials was found in the range of 18–19 nm. The increase in dielectric constant, as well as with moderate loss, was observed in all substituted samples between 0.001 GHz and 1 GHz. The large values of dielectric constant were observed for Al³⁺ and In³⁺ substituted materials at higher frequency. The values of slope (n) reveal that all the materials exhibit frequency dependent ac conductivity. The Cole-Cole plots show the single semicircle for all samples. These semicircles of the Cole-Cole plots indicate that resistance inside the material is due to grains and grain boundaries. The both grain and grain boundaries resistance inside the material may cause large values of dielectric constant as well as the losses in the material. The large values of dielectric constant and impedance with moderate dielectric losses of these materials reflect their significant role in the fabrication of electronic devices as a radiation/microwave absorber or high frequency equipment components. Magnetic analysis shows the large values of magnetization and coercivity for Al³⁺ and In³⁺ substituted samples, which reflect that these materials might be beneficial for the absorption of electromagnetic radiation, formation of multilayer chip inductors and recording/storage purpose.     

Melt-reprocessable linear low-density polyethylene/cyclic olefin copolymer blends with low dielectric constant and low thermal expansion

Insulation materials with low dielectric constants, low coefficients of thermal expansion (CTE), low densities, renewability, and low cost are urgently needed in the fields of communication, control and signal cables. Here we report that combining cyclic olefin copolymer (COC) with linear low-density polyethylene (LLDPE) by melt blending achieves the above goals. The dielectric constant and CTE of LLDPE/COC blends are minimized at 20 wt% COC content, reaching a value of 2.23 at 1000 Hz and 1.21 × 10⁻⁴ K⁻¹, respectively. The density of the blend increases by only 1.6% compared with LLDPE, whereas the tensile modulus increases by 56%, which is conducive to the blends to improve mechanical strength while preserving lightweight. The rheological tests show that the zero-shear viscosity, storage modulus, and loss modulus of the LLDPE/COC blends do not change much compared with pristine LLDPE, maintaining their good melt processability at 160°C. The cyclic rigid structure of COC causes a decrease in CTE, and the increase in free volume between molecular chains is responsible for the reduced dielectric constant. The present work provides a promising route to the design and fabrication of melt-reprocessable polymer composites with low dielectric constant and low thermal expansion.     

预拉伸对硅橡胶介电性能的影响

以液体硅橡胶DC 186为基体,通过控制交联体系的用量制备了不同的硅橡胶薄膜材料,研究了交联程度对硅橡胶材料力学性能影响,研究了预拉伸程度和持续时间对硅橡胶材料介电性能的影响。结果表明,交联程度的增加会降低硅橡胶分子链运动中的能量损耗;由于预拉伸使得分子链上的极性基团活性降低,发生取向极化的概率减小,因此预拉伸程度越高、预拉伸持续时间越长,硅橡胶材料的介电常数越小,低频下的介电损耗越大。     

Untersuchungen zur Langkettenverzweigung in Polyäthylenen

Polyethylene samples of various densities and melt flow indices resulting from different polymerization processes have been investigated with respect to long chain branching (LKV). For that purpose several polymer fractions have been characterized by measurement of weight average molecular weights M_w and intrinsic viscosities [η], the latter ranging from 0,2 to 3,2 with high pressure samples and from 0,2 to 10 with low pressure material. The intrinsic viscosity difference of branched (high pressure) polyethylene compared to linear (low pressure) polyethylene is used as a measure of LKV. With high pressure polyethylene LKV increases with decreasing density. This dependence is strongest within the medium molecular weight range. Samples with varying LKV but constant density can be obtained by appropriate change of polymerization conditions. No LKV has been observed with low pressure polyethylene. This means a marked difference compared to high pressure material of equal density. Branching with low pressure polymers can therefore be ascribed to the short chain type only, which in particular results from copolymerization. Several mathematical approaches have been checked whether or not they can yield suitable information about n, the number of long chain branches per molecule. The best fit with our experimental data is obtained using the expression [η]v/[η]₁ = g^1,3 (n = f(g)) and assuming, that the average concentration of long chain branch points does not depend on molecular weight for fractions of the same sample (n/M = const.). If LKV ist taken into consideration, logarithmic normal molecular weight distributions are obtained for many high pressure polyethylenes (similar to low pressure material). Data are reported in support of the view, that performance characteristics are dependent on LKV. There is some evidence, that melt flow properties of polyethylene are improved with increasing LKV.