Graphene-Based Hybrid Fillers for Rubber Composites.

Graphene and its derivatives have been confirmed to be among the best fillers for rubber due to their excellent properties, such as high mechanical strength, improved interface interaction, and strain-induced crystallization capabilities. Graphene rubber materials can be widely used in tires, shoes, high-barrier conductive seals, electromagnetic shielding seals, shock absorbers, etc. In order to reduce the graphene loading and endow more desirable functions to rubber materials, graphene-based hybrid fillers are extensively employed, which can effectively enhance the performance of rubber composites. This review briefly summarizes the recent research on rubber composites with graphene-based hybrid fillers consisting of carbon black, silica, carbon nanotubes, metal oxide, and one-dimensional nanowires. The preparation methods, performance improvements, and applications of different graphene-based hybrid fillers/rubber composites have been investigated. This study also focuses on methods that can ensure the effectiveness of graphene hybrid fillers in reinforcing rubber composites. Furthermore, the enhanced mechanism of graphene- and graphene derivative-based hybrid fillers in rubber composites is investigated to provide a foundation for future studies.

Ultra-Low Loading of Ultra-Small Fe3 O4 Nanoparticles on Nonmodified CNTs to Improve Green EMI Shielding Capability of Rubber Composites.

From a material design perspective, the incorporation of Fe3 O4 @carbon nanotube (Fe3 O4 @CNT) hybrids is an effective approach for reconciling the contradictions of high shielding and low reflection coefficients, enabling the fabrication of green shielding materials and reducing the secondary electromagnetic wave pollution. However, the installation of Fe3 O4 nanoparticles on nonmodified and nondestructive CNT walls remains a formidable challenge. Herein, a novel strategy for fabricating the above-mentioned Fe3 O4 @CNTs and subsequently assembling segregated Fe3 O4 @CNT networks in natural rubber (NR) matrices is proposed. The advanced and unique structure, magnetism, and lossless conductivity endow the as-obtained Fe3 O4 @CNT/NR with a shielding effectiveness (SE) of 63.8 dB and a low reflection coefficient of 0.24, which indicates a prominent green-shielding capability that surpasses those of previously reported green-shielding materials. Moreover, the specific SE reaches 531 dB cm-1 , exceeding that of those of previously reported carbon/polymer composites. Meanwhile, the outstanding conductivity enables the composite to reach a saturation temperature of ≈95 °C at a driving voltage of 1.5 V with long-term stability. Therefore, the as-fabricated Fe3 O4 @CNT/rubber composites represent an important development in green-shielding materials that are applied in cold environment.

Constructing a Segregated Magnetic Graphene Network in Rubber Composites for Integrating Electromagnetic Interference Shielding Stability and Multi-Sensing Performance.

A flexible, wearable electronic device composed of magnetic iron oxide (Fe3O4)/reduced graphene oxide/natural rubber (MGNR) composites with a segregated network was prepared by electrostatic self-assembly, latex mixing, and in situ reduction. The segregated network offers the composites higher electrical conductivity and more reliable sensing properties. Moreover, the addi-tion of Fe3O4 provides the composites with better electromagnetic interference shielding effectiveness (EMI SE). The EMI shielding property of MGNR composites is more stable under tensile deformation and long-term cycling conditions and has a higher sensitivity to stretch strain compared with the same structure made from reduced graphene oxide/natural rubber (GNR) composites. The EMI SE value of MGNR composites reduces by no more than 2.9% under different tensile permanent deformation, cyclic stretching, and cyclic bending conditions, while that of GNR composites reduces by approximately 16% in the worst case. Additionally, the MGNR composites have a better sensing performance and can maintain stable signals, even in the case of cyclic stretching with a very small strain (0.05%). Furthermore, they can steadily monitor the changes in resistance signals in various human motions such as finger bending, wrist bending, speaking, smiling, and blinking, indicating that the MGNR composites can be used in future wearable electronic flexibility devices.

Construction of a Three-Dimensional BaTiO3 Network for Enhanced Permittivity and Energy Storage of PVDF Composites.

Three-dimensional BaTiO3 (3D BT)/polyvinylidene fluoride (PVDF) composite dielectrics were fabricated by inversely introducing PVDF solution into a continuous 3D BT network, which was simply constructed via the sol-gel method using a cleanroom wiper as a template. The effect of the 3D BT microstructure and content on the dielectric and energy storage properties of the composites were explored. The results showed that 3D BT with a well-connected continuous network and moderate grain sizes could be easily obtained by calcining a barium source containing a wiper template at 1100 °C for 3 h. The as-fabricated 3D BT/PVDF composites with 21.1 wt% content of 3D BT (3DBT-2) exhibited the best comprehensive dielectric and energy storage performances. An enhanced dielectric constant of 25.3 at 100 Hz, which was 2.8 times higher than that of pure PVDF and 1.4 times superior to the conventional nano-BT/PVDF 25 wt% system, was achieved in addition with a low dielectric loss of 0.057 and a moderate dielectric breakdown strength of 73.8 kV·mm-1. In addition, the composite of 3DBT-2 exhibited the highest discharge energy density of 1.6 × 10-3 J·cm-3 under 3 kV·mm-1, which was nearly 4.5 times higher than that of neat PVDF.

Superhydrophobic and Flexible Silver Nanowire-Coated Cellulose Filter Papers with Sputter-Deposited Nickel Nanoparticles for Ultrahigh Electromagnetic Interference Shielding.

Superhydrophobic, flexible, and ultrahigh-performance electromagnetic interference (EMI) shielding papers are of paramount importance to safety and long-term service under external mechanical deformations or other harsh service environments because they fulfill the growing demand for multipurpose materials. Herein, we fabricated multifunctional papers by incorporating sputter-deposited nickel nanoparticles (NiNPs) and a fluorine-containing coating onto cellulose filter papers coated with silver nanowires (AgNWs). AgNW networks with sputter-deposited NiNPs provide outstanding magnetic properties, electrical conductivity, and EMI shielding performance. At an AgNW content of 0.109 vol % and a NiNP content of 0.013 mg/cm2, the resultant papers exhibit a superior EMI shielding effectiveness (SE) of 88.4 dB. Additionally, the fluorine-containing coating endows the resultant papers with a high contact angle of 149.7°. Remarkably, the obtained papers still maintain a high EMI SE even after 1500 bending cycles or immersion in water, salt, or strong alkaline solutions for 2 h, indicating their outstanding mechanical robustness and chemical durability. This work opens a new window for designing and implementing ultrahigh-performance EMI shielding materials.

Robust, flexible, and high-performance electromagnetic interference shielding films with long-lasting service.

It is of great significance for electromagnetic interference (EMI) shielding materials to fulfill long-lasting service requirements. Here, waterborne polyurethane (WPU) was coated on the surface of a silver nanowire (AgNW) network with sputter-deposited nickel nanoparticles (NiNPs) by dip-coating technology to improve their durability. After five dip-coating cycles, a WPU layer nearly coated the whole surface of the hybrid papers, and only a fraction of the metal filler is bare. The resultant hybrid papers exhibit an electrical conductivity of ∼3500 S m-1, remnant magnetization of 0.03 emu g-1, saturation magnetization of 0.10 emu g-1, and coercivity of 256 Oe. On the one hand, the presence of the WPU coating does not affect the shielding effectiveness (SE) of the hybrid papers; on the other hand, the WPU coating enhances the ability to resist tape peeling. Moreover, the resultant hybrid papers still maintain the original SE value (∼80 dB), even after exposure to air for 5 months owing to the isolation effect of the WPU coating, implying long-lasting durability. The results confirm that the obtained hybrid papers can meet the requirements of practical applications.

Electric Heating Behavior of Reduced Oxide Graphene/Carbon Nanotube/Natural Rubber Composites with Macro-Porous Structure and Segregated Filler Network.

Conductive polymer composites with carbonaceous fillers are very attractive and play a significant role in the field of electric heaters owing to their lightweight, corrosion resistance, and easy processing as well as low manufacturing cost. In this study, lightweight reduced oxide graphene/carbon nanotube/natural rubber (rGO/CNT/NR) composites were fabricated by a facile and cost-effective approach, which consists of rGO assembling on rubber latex particles and hydrogels formation due to the interaction network established between carbonaceous fillers and subsequent mild-drying of the resulting hydrogels. Thanks to the amphiphilic nature of GO sheets, which can serve as a surfactant, the hydrophobic CNTs were easily dispersed into water under ultrasound. On the basis of both the high stable rGO and CNTs suspension and the assembling of rGO on rubber latex, a three-dimensional segregated network of CNT and rGO were easily constructed in macro-porous composites. Either the segregated network and macro-porous structure endowed the resulting composites with low density (0.45 g cm-3), high electrical conductivity (0.60 S m-1), and excellent electric heating behavior, when the weight content of rGO and CNTs are 0.5% and 2.5%, respectively. For electric heating behavior, the steady-state temperature of the above composites reaches 69.1 °C at an input voltage of 15 V.

Well-aligned MXene/chitosan films with humidity response for high-performance electromagnetic interference shielding.

MXene/polymer composites have been used as electromagnetic interference (EMI) shielding materials due to metallic conductivity of MXene recently. Considering the biodegradability, nontoxic effects and renewable nature of biomass polymer, chitosan (CS)/MXene films with an EMI shielding function were prepared by vacuum assisted filtration. The well-aligned Ti3C2Tx layers endow CS/MXene films with excellent electrical conductivity, which is association with air humidity, and EMI shielding property. The 37-micron-thick CS/MXene film at a T3C2Tx content of 75 % exhibits a high EMI shielding effectiveness of ∼ 34.7 ± 0.2 dB due to the excellent electrical conductivity of CS/MXene films (∼ 1402 ± 70 S m-1) and multiple internal reflections of Ti3C2Tx flakes. Moreover, the specific shielding effectiveness of 13-micron-thick CS/MXene film at a T3C2Tx content of 50 % reaches to 15153.9 ± 153 dB cm-1, outperforming the reported biomass-based EMI shielding composites in the X-band frequency. Due to these advantages, the film shows potential applications in the next-generation EMI shielding materials.

An anisotropic layer-by-layer carbon nanotube/boron nitride/rubber composite and its application in electromagnetic shielding.

Multifunctional polymer composites with anisotropic properties are attracting interest as they fulfil the growing demand of multitasking materials. In this work, anisotropic polymer composites have been fabricated by combining the layer-by-layer (LBL) filtration method with the alternative assembling of carbon nanotubes (CNTs) and hexagonal boron nitride flakes (hBN) on natural rubber latex particles (NR). The layered composites exhibit anisotropic thermal and electrical conductivities, which are tailored through the layer formulations. The best composite consists of four layers of NR modified with 8 phr (parts per Hundred Rubber) CNTs (∼7.4 wt%) and four alternate layers with 12 phr hBN (∼10.7 wt%). The composites exhibit an electromagnetic interference (EMI) shielding effectiveness of 22.41 ± 0.14 dB mm-1 at 10.3 GHz and a thermal conductivity equal to 0.25 W m-1 K-1. Furthermore, when the layered composite is used as an electrical thermal heater the surface reaches a stable temperature of ∼103 °C in approx. 2 min, with an input bias of 2.5 V.

Facile Fabrication of a Novel PZT@PPy Aerogel/Epoxy Resin Composite with Improved Damping Property.

A novel lead zirconate titanate@polypyrrole (PZT@PPy) aerogel (PPA) was fabricated via in-situ polymerization and subsequent freeze-drying method. The porous PPA was then saturated with epoxy resin to obtain the PPA/epoxy composite (PPAE) by a simple vacuum filling method. In this way, the filler content and dispersion uniformity are well guaranteed, which is in favor of improving the damping and mechanical properties of composites. The morphology and structure of PPAs were investigated using XRD, SEM, EDS and nitrogen absorption and desorption measurements. The results showed that the PPA possessed a three-dimensional porous structure with uniform lead zirconate titanate (PZT) distribution. The influence of PZT content on the damping property of PPAE composite was investigated by dynamic mechanical analysis (DMA). PPAE-75 (i.e., the mass ratio of PZT to PPy is 75 wt %) exhibited the maximum damping loss factor value, 360% higher than that of the epoxy matrix, suggesting good structural damping performance.

Enhancing the EMI shielding of natural rubber-based supercritical CO2 foams by exploiting their porous morphology and CNT segregated networks.

Natural rubber/carbon nanotubes composite foams (F-NR/CNTs) with high electrical conductivity and excellent electromagnetic interference (EMI) performance were developed through a multi-step process including: (a) CNTs assembled on natural rubber latex particles, (b) pre-crosslinking of natural rubber, (c) supercritical carbon dioxide foaming of pre-crosslinked composite samples and (d) post-crosslinking of foamed composite samples. A closed-cell porous structure and a segregated CNT network are clearly observed in the resulting foams. Due to this morphology, F-NR/CNTs exhibit low density, good mechanical properties, and high electrical conductivity. Owing to the multiple radiation reflections and scattering between the cell-matrix interfaces, the composite foams presented an excellent specific shielding effectiveness (SSE) of 312.69 dB cm2 g-1 for F-NR/CNTs containing 6.4 wt% of CNTs, which is significantly higher than those already published for rubber composites containing comparable filler content. Furthermore, the analysis of EMI SE highlights that absorption efficiency is more significant than reflection efficiency, implying that most of the incident electromagnetic radiation is dissipated in the form of heat. This work provides the fundamentals for the design of innovative light weight and efficient EMI shielding foams characterized by a three-dimensional segregated CNT network with huge potential for use in the electronics and aerospace industries.

Tailoring assembly of reduced graphene oxide nanosheets to control gas barrier properties of natural rubber nanocomposites.

Self-assembling of reduced graphene oxide platelets, as a tailored interconnected network within a natural rubber matrix, is proposed as a mean for obtaining nanocomposites with improved gas barrier, as compared to neat natural rubber. Interestingly, this nanocomposite structure results to be much more effective than homogeneous dispersion of graphene platelike particles, even at low graphene loadings. Such behavior is interpreted on the grounds of a theoretical model describing permeability of heterogeneous systems specifically accounting for self-segregated graphene morphology.