Enhanced microwave absorbing performance of hydrogenated acrylonitrile–butadiene rubber/multi-walled carbon nanotube composites by in situ prepared rare earth acrylates

Rare earth oxides (REO = Gd₂O₃, Dy₂O₃, Tm₂O₃) and acrylic acid (AA) were in situ reacted in hydrogenated acrylonitrile–butadiene rubber (HNBR) to prepare HNBR/multi-walled carbon nanotube (MWCNT)/REO/AA composites. The HNBR/MWCNT/REO/AA composites have higher permittivity and dielectric loss than HNBR/MWCNT composite, leading to significantly enhanced microwave absorbing performance of the HNBR/MWCNT/REO/AA composites. Dielectric permittivity analysis reveals that the HNBR/MWCNT/REO/AA composites have longer dielectric relaxation time and higher conductivity than the HNBR/MWCNT composite. The HNBR/MWCNT composite has the minimum reflection loss of −15.1 dB, while the HNBR/MWCNT/REO/AA composites have the minimum reflection loss of −48.8 dB. The improvement of microwave absorbing performance is attributed to the stronger interfacial polarization and higher conductivity after formation of in situ prepared rare earth acrylates.     

Morphological changes of carbon nanotubes in polyethylene matrices under oscillatory tests as determined by dielectrical measurements

By combining a high sensitive dielectric sensor into a parallel plate rheometer, the time evolution of the dielectric properties of polyethylene/carbon nanotube composites was measured in the molten state under oscillatory shear. Composites with single- (SWCNT) or multiwall (MWCNT) carbon nanotubes initially decrease its conductivity proportional to the oscillatory shear-strain applied. After this initial drop, some composites increase the conductivity under these non-quiescent conditions reflecting a possible shear-induced agglomeration process. The latter based on the complex permittivity spectrum showing a shortening in the CNT-CNT distances in these composites after shear. At concentrations below the electrical percolation threshold, the presence of both SWCNTs and MWCNTs reduces the DC conductivity of the molten matrices. This result shows that carbon nanotubes can act as a scavenger for impurities or additives present in commercial polyethylenes.     

Electrical properties of polyvinylidene fluoride (PVDF)/multi-walled carbon nanotube (MWCNT) semi-transparent composites: Modelling of DC conductivity

Transparent conductive composites can be achieved from PVDF–MWCNT at very low concentration of MWCNT. These composites show different degree of UV–Visible radiation absorption depending on MWCNT concentration in composites. The composition dependent dielectric properties and AC conductivity were also measured for these composites. Properties like AC conductivity, dielectric constant and loss are increasing with filler concentration. The variations of DC conductivity against composition and temperature are also reported. The electrical hysteresis and electrical set are observed for PVDF–MWCNT composites when subjected to heating–cooling cycle. The validity of different theoretical models depicting percolation threshold with respect to DC conductivity was tested for these composites.     

Electrical conductivity and shielding effectiveness of poly(trimethylene terephthalate)/multiwalled carbon nanotube composites

Poly(trimethylene terephthalate) (PTT)/multiwalled carbon nanotube (MWCNT) composites have been fabricated to evaluate the potential of PTT composites as electromagnetic interference (EMI) shielding material. The room temperature electrical conductivity, complex permittivity, and shielding effectiveness (SE) of PTT/MWCNT composites were studied in the frequency range of 8.2–12.4 GHz (X-band). The dc conductivity (σ) of composites increased with increasing MWCNT loading and a typical percolation behavior was observed at 0.48 vol% MWCNT loading. The highest EMI SE of PTT/MWCNT composites was ~23 decibel (dB) at 4.76 vol% MWCNT loading which suggest that these composites can be used as light weight EMI shielding materials. The correlation among the SE, complex permittivity, and electrical conductivity was also studied. The EMI shielding mechanism of PTT/MWCNT composites was studied by resolving the total EMI SE into absorption and reflection loss.     

Three-dimensional carbon nanotube based polymer composites for thermal management

In this study, the porous multiwall carbon nanotube (MWCNT) foams possessing three-dimensional (3D) scaffold structures have been introduced into polydimethylsiloxane (PDMS) for enhancing the overall thermal conductivity (TC). This unique interconnected structure of freeze-dried MWCNT foams can provide thermally conductive pathways leading to higher TC. The TC of 3D MWCNT and PDMS composites can reach 0.82 W/m K, which is about 455% that of pure PDMS, and 300% higher than that of composites prepared from traditional blending process. The obtained polymer composites not only exhibit superior mechanical properties but also dimensional stability. To evaluate the performance of thermal management, the LED modulus incorporated with the 3D MWCNT/PDMS composite as heat sink is also fabricated. The composites display much faster and higher temperature rise than the pristine PDMS matrix, suggestive of its better thermal dissipation. These results imply that the as-developed 3D-MWCNT/PDMS composite can be a good candidate in thermal interface for thermal management of electronic devices.     

Electromagnetic characteristic and microwave absorbing performance of different carbon-based hydrogenated acrylonitrile–butadiene rubber composites

Hydrogenated acrylonitrile–butadiene rubber (HNBR) was mixed with carbon fiber (CF), conductive carbon black (CCB) and multi-walled carbon nanotubes (MWCNT) to prepare microwave absorbing composites, their complex permittivity was measured in microwave frequencies (2–18 GHz), and their electromagnetic characteristics and microwave absorbing performance were studied. The real part and imaginary part of permittivity of the composites increased with increasing carbon filler loading, showing dependency on filler type. The microwave reflection loss of the composites also depended on the loading and type of fillers. The matching thickness of the absorber layer decreased with increasing permittivity, while the matching frequency decreased with increasing layer thickness. The minimum reflection loss was −49.3 dB for HNBR/MWCNT (100/10) composite, while −13.1 dB for HNBR/CCB (100/15) composite and −7.1 dB for HNBR/CF (100/30) composite. The efficient microwave absorption of HNBR/MWCNT composites is accounted from high conduction loss and dielectric relaxation of MWCNT, and strong interface scattering.     

Dielectric constant enhancement in a silicone elastomer filled with lead magnesium niobate–lead titanate

Lead magnesium niobate–lead titanate (PMN–PT) ferroelectric powder was used to develop a particulated composite based on a silicone elastomer matrix, with improved dielectric permittivity. The filler was characterised by X-ray diffraction and scanning electron microscopy. Complex dielectric permittivity (10–10⁸ Hz) and tensile mechanical properties (elastic modulus and ultimate stress) of composites at various filler contents (up to 30% by vol.) were compared with those of the neat silicone elastomer. Both the dielectric constant and loss factor regularly increased with the filler content. The elastic modulus increased with a lower rate than that of the dielectric constant. Even though the addition of filler resulted in a detriment of both toughness, ultimate stress and elongation at break, a good stretchability was still retained, as elongation ratios greater than 3 were possible at the highest filler content. Several dielectric models were compared to the experimental data and the best match was achieved by the Bruggeman model, which can be used as a predictive rule for different volume contents of filler.     

Electromechanical instability and snap-through instability of dielectric elastomers undergoing polarization saturation

By applying a voltage, electric charge will be induced on the surface of dielectric elastomers. Generally, the charge increases with the level of voltage. When the voltage reaches to a certain value, the charge would not increase any more due to the polarization saturation of dielectric materials. In this paper, a thermodynamic constitutive model, combined both the nonlinear dielectric and hyperelastic behavior as dielectric elastomers undergoing polarization saturation, has been developed. Analytical solutions have been obtained for situations incorporating strain-stiffening effect, electromechanical instability and snap-through instability. The numerical results reveal the marked influence of the extension and polarization saturation limits of elastomer material on its electromechanical instability and the snap-through instability. The developed constitutive model would be helpful in future research of dielectric elastomer based high-performance transducers.     

TiO2-nanorod decorated carbon nanotubes for high-permittivity and low-dielectric-loss polystyrene composites

Polymer composites with high permittivity and low dielectric loss are highly desirable in electronic and electrical industry. Adding conductive fillers could significantly increase the permittivity of a polymer. However, polymer composites containing conductive fillers often exhibit very high dielectric loss due to their large electrical conduction or leakage currents. In this work, by engineering TiO₂-nanorod-decorated multi-walled carbon nanotubes (TD-CNTs), polystyrene (PS) composite with high permittivity and low dielectric loss have been successfully prepared. The composite containing of 17.2 vol.% TD-CNTs has a permittivity of 37 at 1 kHz, which is 13.7 times higher than that of the pure PS (2.7), while the dielectric loss still remains at a low value below 0.11. The dielectric properties of the composites are closely related to the length of CNTs and the loading level of TiO₂-nanorods on the CNT surfaces.     

Preparation and dielectric properties of a polyurethane elastomer filled with resol-derived ordered mesoporous carbon

This study deals with the preparation and dielectric properties of polyurethane (PU) elastomer films by resol-derived ordered mesoporous carbon (OMC) nanopowder incorporation in the PU polymer matrix. Resol-derived OMC with a 2D hexagonal mesoporous carbon framework is used as conducting fillers to achieve homogeneous dispersion and favorable interfacial interactions in the polymer matrix. The dielectric properties depend on the applied field frequency and the carbon filler weight fraction. The carbon fraction has little effect on the relative permittivity. The relative permittivity of all the PU-OMC composites increases with the decline of frequency. Incorporating a small amount of OMC into the PU polymer had no influence on the dielectric loss. Along with the increasing carbon fraction above the percolation threshold, dielectric loss of PU-OMC composites increases exponentially in the low frequency range. PU-0.75 wt% OMC composite possesses the best dielectric properties, and the obtained relative permittivity and dielectric loss at 1 kHz is 9.59 and 0.03018, respectively.     

A Liquid‐Metal–Elastomer Nanocomposite for Stretchable Dielectric Materials

Stretchable high‐dielectric‐constant materials are crucial for electronic applications in emerging domains such as wearable computing and soft robotics. While previous efforts have shown promising materials architectures in the form of dielectric nano‐/microinclusions embedded in stretchable matrices, the limited mechanical compliance of these materials significantly limits their practical application as soft energy‐harvesting/storage transducers and actuators. Here, a class of liquid metal (LM)–elastomer nanocomposites is presented with elastic and dielectric properties that make them uniquely suited for applications in soft‐matter engineering. In particular, the role of droplet size is examined and it is found that embedding an elastomer with a polydisperse distribution of nanoscale LM inclusions can enhance its electrical permittivity without significantly degrading its elastic compliance, stretchability, or dielectric breakdown strength. In contrast, elastomers embedded with microscale droplets exhibit similar improvements in permittivity but a dramatic reduction in breakdown strength. The unique enabling properties and practicality of LM–elastomer nanocomposites for use in soft machines and electronics is demonstrated through enhancements in performance of a dielectric elastomer actuator and energy‐harvesting transducer.     

Improvement of electrostrictive properties of a polyether-based polyurethane elastomer filled with conductive carbon black

The electrostrictive properties of a polyether-based polyurethane elastomer and its corresponding composites filled with conductive carbon black (CB) were studied by measuring the thickness strain S_Z induced by external electric fields E. For films with thicknesses of approximately 50 μm, the apparent electrostrictive coefficient M was measured at low electric fields, E ? 4 V/μm, and different CB contents (up to a volume fraction of 2%). Dielectric measurements in AC mode were performed in order to determine the percolation threshold f_c, which was 1.25 v%. This optimal volume fraction yielded a remarkable threefold increase in M, associated with an increase of the dielectric constant by a factor 7, in comparison with pure PU. This enhancement of the electric field-induced strain and apparent electrostriction was mainly triggered by an increase of the dielectric constant, even if the intrinsic electrostriction coefficient Q was decreased. The nanocomposites thus seem to be very attractive for low-frequency electromechanical applications. Above f_c, their conductivity was raised and their electrostrictive activity lost. Finally, there is a good agreement between the experimentally determined dependence on the CB content of the M coefficient and the theoretical estimation calculated from dielectric and mechanical measurements.     

Layered dielectric–magnetic composite structures for Rf-applications

In this paper multilayer magnetic–dielectric composite structures for high frequency applications are introduced. The 0–3 type dielectric and magnetic composites with homogeneously distributed ceramic inclusions were fabricated by mixing extrusion and injection moulding. Magnetic Yttrium Iron Garnet (YIG) and Z-type Hexaferrite (HexaZ) as well as paraelectric Barium Strontium Titanate (BST) powders were used to enhance the permittivity and permeability of the composites. The magnetic–dielectric multilayer composites were constructed by hot-laminating magnetic and dielectric layers in turn to create a solid 2-2 type composite structure. The microstructure, high frequency dielectric and magnetic properties of individual layers and 2-2 composites were investigated and measured. The measurement results indicate that such multimaterial multilayer structures are good candidates for components with reduced dielectric and magnetic losses. Moreover, the observed good frequency stability and the cut-off frequencies above 1 GHz suggested that the composites could be utilized in, e.g., sophisticated functional circuit boards and RF devices.     

Thermal conductivity of polymer composites based on the length of multi-walled carbon nanotubes

The anisotropic development of thermal conductivity in polymer composites was evaluated by measuring the isotropic, in-plane and through-plane thermal conductivities of composites containing length-adjusted short and long multi-walled CNTs (MWCNTs). The thermal conductivities of the composites were relatively low irrespective of the MWCNT length due to their high contact resistance and high interfacial resistance to polymer resins, considering the high thermal conductivity of MWCNTs. The isotropic and in-plane thermal conductivities of long-MWCNT-based composites were higher than those of short-MWCNT-based ones and the trend can accurately be calculated using the modified Mori-Tanaka theory. The in-plane thermal conductivity of composites with 2 wt% long MWCNTs was increased to 1.27 W/m·K. The length of MWCNTs in polymer composites is an important physical factor in determining the anisotropic thermal conductivity and must be considered for theoretical simulations. The thermal conductivity of MWCNT polymer composites can be effectively controlled in the processing direction by adjusting the length of the MWCNT filler.     

碳纳米管的偶联剂修饰及其在环氧树脂复合材料中的应用

为了在环氧树脂( EP) 复合材料中改善碳纳米管(CNTs) 的分散性和获得优良的界面特性, 利用Fenton 试剂对CNTs 进行了羟基化处理, 然后分别利用硅烷偶联剂KH550、KH560、KH570 和钛酸酯偶联剂NDZ201对羟基化CNTs 进行表面修饰, 通过SEM、TGA、DSC 和阻抗分析仪研究偶联剂修饰对CNTs/ EP 复合材料性能的影响。实验结果表明: Fenton 试剂和4 种偶联剂修饰都能显著改善CNTs 在复合材料中的分散性, 提高EP的玻璃化温度(T_g) 和热稳定性, 其中偶联剂修饰比Fenton 试剂处理更有效; 然而这些改性却大幅度降低了复合材料的导电性能、介电常数以及介电损耗。4 种偶联剂中, KH560 对应的复合材料的T_g最高, 热稳定性和导电性能最好, 同时具有较高的介电常数和较低的介电损耗。      

A comparative study on the electrical,thermal and mechanical properties of ethylene–octene copolymer based composites with carbon fillers

Conducting polymer composites (CPC) were prepared with an ethylene–octene copolymer (EOC) matrix and with either carbon fibers (CFs) or multiwall carbon nanotubes (MWCNTs) as fillers. Their electrical and thermal conductivities, mechanical properties and thermal stabilities were evaluated and compared. CF/EOC composites showed percolation behavior at a lower filler level (5 wt.%) than the MWCNT/EOC composites (10 wt.%) did. Alternating current (AC) conductivity and real part of permittivity (dielectric constant) of these composites were found to be frequency-dependent. Dimensions and electrical conductivities of individual fillers have a great influence on the conductivities of the composites. CF/EOC composites possessed higher conductivity than the MWCNT-composites at all concentrations, due to the higher length and diameter of the CF filler. Both electrical and thermal conductivities were observed to increase with increasing filler level. Tensile moduli and thermal stabilities of both (CF/EOC and MWCNT/EOC) composites increase with rising filler content. Improvements in conductivities and mechanical properties were achieved without any significant increase in the hardness of the composites; therefore, they can be potentially used in pressure/strain sensors. Thermoelectric behavior of the composites was also studied. Accordingly, CF and MWCNT fillers are versatile and playing also other roles in their composites than just being conducting fillers.     

Microwave Absorption and Shielding Property of Composites with FeSiAl and Carbonous Materials as Filler

Silicone rubber composites filled with FeSiAl alloys and multi-walled carbon nanotubes(MWCNT)/graphite have been prepared for the first time by a coating process.The complex permittivity and permeability of the composites were measured with a vector network analyzer in a 1-4 GHz frequency range,and the DC electric conductivity was measured by a standard four-point contact method.These parameters were then used to calculate the reflection loss(RL) and shielding effectiveness(SE) of the composites.The results showed that the added MWCNT increased the permittivity and permeability of composites in the L-band,while the added graphite increased only the permittivity.The variation lies in the interactions between two carbonous absorbents.Addition of 1 wt% MWCNT enhanced the RL in the L-band(minimum 5.7 dB at 1 mm,7.3 dB at 1.5 mm),while the addition of graphite did not.Addition of MWCNT as well as graphite reinforced the shielding property of the composites(maximum SE 13.3 dB at 1 mm,18.3 dB at 1.5 mm) owing to the increase of conductivity.The addition of these carbonous materials could hold the promise of enforcing the absorption and shielding property of the absorbers.     

Large dielectric constant of the chemically purified carbon nanotube/polymer composites

The chemically purified multiwalled carbon nanotube/poly(vinylidene fluoride) (MWCNT/PVDF) composites were fabricated. Raman spectroscopy and transmission electron microscopy micrographs indicated that the catalysts metal particles and amorphous carbon had been removed from the purified MWCNTs. The percolation threshold of the composites is relatively large, about 3.8 vol.%. The most important result is that the dielectric constant of the composites is enhanced remarkably, and the dielectric constant of 3600 is obtained in the composite with 8 vol.% purified MWCNT at 1 kHz. The large dielectric constant can be attributed to the preparation procedure and the interface effect between the MWCNTs and the polymer.     

Enhanced polarization in zirconia-P(VDF-TrFE) laminar composite dielectrics

Zirconia-P(VDF-TrFE) double-layered laminar composites are experimentally investigated to understand inorganic–organic interfacial effects in composite dielectrics. The DC and AC electrical response of the individual phases were characterized in addition to the zirconia-P(VDF-TrFE) composite. The measured real part of permittivity for the laminar composite is found to be higher than theoretically calculated values using series mixing rules for zirconia and P(VDF-TrFE). Additional polarization of the composite structure can be attributed to either the presence of interfacial polarization of zirconia and P(VDF-TrFE) or modification of polymer. Impedance spectroscopy has shown that dielectric properties of laminar composites are dominated by zirconia thin films in low frequency region. The impedance spectroscopy shows that zirconia blocks charge carrier motion and hence partially contribute towards additional interfacial polarization in the laminar composite. The dielectric response of the laminar composite was also modeled through a Maxwell–Wagner interfacial polarization mechanism, which was found to inadequately describe the polarization response. Equivalent circuit modeling of the composite has revealed an additional interfacial circuit element for the additional polarization, suggesting a structurally modified polymer at the interface.     

Structure–property relationships in isotactic polypropylene/multi-walled carbon nanotubes nanocomposites

In this work, the influence of multi-walled carbon nanotubes (MWCNT) on electrical, thermal and mechanical properties of CNT reinforced isotactic polypropylene (iPP) nanocomposites is studied. The composites were obtained by diluting a masterbatch of 20 wt.% MWCNT with a low viscous iPP, using melt mixing. The morphology of the prepared samples was examined through SEM, Raman and XRD measurements. The effect of MWCNT addition on the thermal transitions of the iPP was investigated by differential scanning calorimetry (DSC) measurements. Significant changes are reported in the crystallization behavior of the matrix on addition of carbon nanotubes: increase of the degree of crystallinity, as well as appearance of a new crystallization peak (owing to trans-crystallinity). Dynamic mechanical analysis (DMA) studies revealed an enhancement of the storage modulus, in the glassy state, up to 86%. Furthermore, broadband dielectric relaxation spectroscopy (DRS) was employed to study the electrical and dielectric properties of the nanocomposites. The electrical percolation threshold was calculated 0.6–0.7 vol.% MWCNT from both dc conductivity and dielectric constant values. This value is lower than previous mentioned ones in literature in similar systems. In conclusion, this works provides a simple and quick way for the preparation of PP/MWCNT nanocomposites with low electrical percolation threshold and significantly enhanced mechanical properties.