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.

3D Printing Self-Healing and Self-Adhesive Elastomers for Wearable Electronics in Amphibious Environments.

To meet the demands of challenging usage scenarios, there is an increasing need for flexible electronic skins that can operate properly not only in terrestrial environments but also extend to complex aquatic conditions. In this study, we develop an elastomer by incorporating dynamic urea bonds and hydrogen bonds into the polydimethylsiloxane backbone, which exhibits excellent autonomous self-healing and reversible adhesive performance in both dry and wet environments. A multifunctional flexible sensor with excellent sensing stability, amphibious self-healing capacity, and amphibious self-adhesive performance is fabricated through solvent-free 3D printing. The sensor has a high sensing sensitivity (GF = 45.1) and a low strain response threshold (0.25%) and can be used to detect small human movements and physiological activities, such as muscle movement, joint movement, respiration, and heartbeat. The wireless wearable sensing system assembled by coupling this device with a bluetooth transmission system is suitable for monitoring strenuous human movement in amphibious environments, such as playing basketball, cycling, running (terrestrial environments), and swimming (aquatic environments). The design strategy provides insights into enhancing the self-healing and self-adhesive properties of soft materials and promises a prospective avenue for fabricating flexible electronic skin that can work properly in amphibious environments.

Enhanced properties of gelatin films incorporated with TiO2-loaded reduced graphene oxide aerogel microspheres for active food packaging applications.

The synergistic effect of graphene sheets and titanium dioxide nanoparticles (TiO2) hybrid fillers can improve the antibacterial, mechanical, and barrier properties of gelatin (GL), making it more suitable to be used in the food packaging application. However, the uneven dispersion and aggregation of the hybrid fillers restrict its performance for further application. In order to achieve the above superior properties, reduced graphene oxide aerogel microspheres (rGOAMs) loaded with TiO2 (rGOAMs@TiO2) were successfully prepared using one-step hydrothermal process by reducing titanium sulfate into TiO2 on the framework of rGOAMs, followed by effective dispersion in the GL matrix to form nanocomposites (rGOAMs@TiO2/GL) through simultaneous ultrasonication and mechanical stirring, as well as an ultrasonic cell grinder process. Incorporating a mere 0.8 wt% of rGOAMs@TiO2 effectively improved the mechanical, antibacterial, UV light barrier, thermal stability, hydrophobicity, and water vapor barrier properties of the GL. Compared with the composites made of rGOAMs, TiO2, and GL (rGOAMs/TiO2/GL), rGOAMs@TiO2/GL composites showed stronger filler-matrix interactions, better filler dispersion, and lower TiO2 particle aggregation, suggesting superiority compared to rGOAMs/TiO2/GL composites at the same filler content. This innovative method of mixing GL with rGOAMs@TiO2 holds great promise for enhancing the suitability of GL in active food packaging applications.

Liquid Crystal Elastomer Artificial Tendrils with Asymmetric Core-Sheath Structure Showing Evolutionary Biomimetic Locomotion.

The sophisticated and complex haptonastic movements in response to environmental-stimuli of living organisms have always fascinated scientists. However, how to fundamentally mimic the sophisticated hierarchical architectures of living organisms to provide the artificial counterparts with similar or even beyond-natural functions based on the underlying mechanism remains a major scientific challenge. Here,  liquid crystal elastomer (LCE) artificial tendrils showing evolutionary biomimetic locomotion are developed following the structure-function principle that is used in nature to grow climbing plants. These elaborately designed tendril-like LCE actuators possess an asymmetric core-sheath architecture which shows a higher-to-lower transition in the degree of LC orientation from the sheath-to-core layer across the semi-ellipse cross-section. Upon heating and cooling, the LCE artificial tendril can undergo reversible tendril-like shape-morphing behaviors, such as helical coiling/winding, and perversion. The fundamental mechanism of the helical shape-morphing of the artificial tendril is revealed by using theoretical models and finite element simulations. Besides, the incorporation of metal-ligand coordination into the LCE network provides the artificial tendril with reconfigurable shape-morphing performances such as helical transitions and rotational deformations. Finally, the abilities of helical and rotational deformations are integrated into a new reprogrammed flagellum-like architecture to perform evolutionary locomotion mimicking the haptonastic movements of the natural flagellum.

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.

Optimization of Piezoresistive Response of Elastomeric Porous Structures Based on Carbon-Based Hybrid Fillers Created by Selective Laser Sintering.

Recently, piezoresistive sensors made by 3D printing have gained considerable interest in the field of wearable electronics due to their ultralight nature, high compressibility, robustness, and excellent electromechanical properties. In this work, building on previous results on the Selective Laser Sintering (SLS) of porous systems based on thermoplastic polyurethane (TPU) and graphene (GE)/carbon nanotubes (MWCNT) as carbon conductive fillers, the effect of variables such as thickness, diameter, and porosity of 3D printed disks is thoroughly studied with the aim of optimizing their piezoresistive performance. The resulting system is a disk with a diameter of 13 mm and a thickness of 0.3 mm endowed with optimal reproducibility, sensitivity, and linearity of the electrical signal. Dynamic compressive strength tests conducted on the proposed 3D printed sensors reveal a linear piezoresistive response in the range of 0.1-2 N compressive load. In addition, the optimized system is characterized at a high load frequency (2 Hz), and the stability and sensitivity of the electrical signal are evaluated. Finally, an application test demonstrates the ability of this system to be used as a real-time wearable pressure sensor for applications in prosthetics, consumer products, and personalized health-monitoring systems.

Selective Laser Sintering of Polydimethylsiloxane Composites.

Conductive silicone elastomer carbon nanotubes (CNTs) composites possess potential applications in a variety of fields, including electronic skin, wearable electronics, and human motion detection. Based on a novel self-made covalent adaptable network (CANs) of polydimethylsiloxane (PDMS) containg dynamic steric-hindrance pyrazole urea bond (PDMS-CANs), CNTs wrapped PDMS-CANs (CNTs@PDMS-CANs) powders were prepared by a liquid phase adsorption and deposition, and were successfully used for selective laser sintering (SLS) three-dimensional printing. SLS-printed PDMS-CANs/CNTs nanocomposites possess high electrical conductivity and low percolation threshold as SLS is one kind of quasi-static processing, which leads to the formation of conductive segregated CNTs network by using the PDMS powders with special CNTs wrapped structure. The introduction of dynamic pyrazole urea bond endows the materials self-healing capability under electrothermal and photothermal stimulus. In addition, due to the resistance difference of the damaged and intact areas, crack diagnosing can be realized by infrared thermograph under electricity. In an application demonstration in strain sensor, the composite exhibits a regular cyclic electrical resistance change at cyclic compression and bending, indicating a relative high reliability.

Synthesis and Electrical Percolation of Highly Amorphous Polyvinyl Alcohol/Reduced Graphene Oxide Nanocomposite.

Polyvinyl alcohol is the most commercially water-soluble biodegradable polymer, and it is in use for a wide range of applications. It shows good compatibility with most inorganic/organic fillers, and enhanced composites may be prepared without the need to introduce coupling agents and interfacial modifiers. The patented high amorphous polyvinyl alcohol (HAVOH), commercialized with the trade name G-Polymer, can be easily dispersed in water and melt processed. HAVOH is particularly suitable for extrusion and can be used as a matrix to disperse nanocomposites with different properties. In this work, the optimization of the synthesis and characterization of HAVOH/reduced graphene oxide (rGO) nanocomposite obtained by the solution blending process of HAVOH and Graphene Oxide (GO) water solutions and 'in situ' reduction of GO is studied. The produced nanocomposite presents a low percolation threshold (~1.7 wt%) and high electrical conductivity (up to 11 S/m) due to the uniform dispersion in the polymer matrix as a result of the solution blending process and the good reduction level of GO. In consideration of HAVOH processability, the conductivity obtained by using rGO as filler, and the low percolation threshold, the nanocomposite presented here is a good candidate for the 3D printing of a conductive structure.

Robust and recyclable graphene/chitosan composite aerogel microspheres for adsorption of oil pollutants from water.

Despite recent progress in graphene-based aerogels, challenges such as low mechanical strength and adsorption efficiency are still remaining. Here the reduced graphene oxide (rGO)/chitosan (CS) composite aerogel microspheres (rGCAMs) with center-diverging microchannel structures were developed by electrospraying and freeze-drying method. The optimized rGCAMs exhibit a high Young's modulus of 197 kPa and can support ~75,000 times its own weight, due to the cross-linking of CS by glutaraldehyde. Meanwhile, the rGCAMs can maintain high adsorption capacity for 15 cyclic tests due to its excellent mechanical strength. The oil adsorption kinetics and isotherms of rGCAMs follow the pseudo-second-order kinetic equation and the Langmuir model, respectively. The whole adsorption process is influenced by the oil diffusion in the liquid matrix and also in the intra-particle of aerogel microspheres. Moreover, rGCAMs can also be used to separate both surfactant-stabilized water-in-oil and oil-in-water emulsions through demulsification. The high-strength, recyclable and separation-efficient rGCAMs can be a potential candidate for oily wastewater treatment.

The Effect of the 3D Nanoarchitecture and Ni-Promotion on the Hydrogen Evolution Reaction in MoS2 /Reduced GO Aerogel Hybrid Microspheres Produced by a Simple One-Pot Electrospraying Procedure.

The transition toward renewable energy sources requires low-cost, efficient, and durable electrocatalysts for green H2 production. Herein, an easy and highly scalable method to prepare MoS2 nanoparticles embedded in 3D partially reduced (pr) graphene oxide (GO) aerogel microspheres (MoS2 /prGOAMs) with controlled morphology and composition is described. Given their peculiar center-diverging mesoporous structure, which allows easy access to the active sites and optimal mass transport, and their efficient electron transfer facilitated by the intimate contact between the MoS2 and the 3D connected highly conductive pr-GO sheets, these materials exhibit a remarkable electrocatalytic activity in the hydrogen evolution reaction (HER). Ni atoms, either as single Ni atoms or NiO aggregates are then introduced in the MoS2 /prGOAMs hybrids, to facilitate water dissociation, which is the slowest step in alkaline HER, producing a bifunctional catalyst. After optimization, Ni-promoted MoS2 /prGOAMs obtained at 500 °C reach a remarkable η10 (overpotential at 10 mA cm-2 ) of 160 mV in 1 m KOH and 174 mV in 0.5 m H2 SO4 . Moreover, after chronopotentiometry tests (15 h) at a current density of 10 mA cm-2 , the η10 value improves to 147 mV in alkaline conditions, indicating an exceptional stability.

Progress in Utilizing Dynamic Bonds to Fabricate Structurally Adaptive Self-Healing, Shape Memory, and Liquid Crystal Polymers.

Stimuli-responsive structurally dynamic polymers are capable of mimicking the biological systems to adapt themselves to the surrounding environmental changes and subsequently exhibiting a wide range of responses ranging from self-healing to complex shape-morphing. Dynamic self-healing polymers (SHPs), shape-memory polymers (SMPs), and liquid crystal elastomers (LCEs), which are three representative examples of stimuli-responsive structurally dynamic polymers, have been attracting broad and growing interest in recent years because of their potential applications in the fields of electronic skin, sensors, soft robots, artificial muscles, and so on. Recent advances and challenges in the developments toward dynamic SHPs, SMPs, and LCEs are reviewed, focusing on the chemistry strategies and the dynamic reaction mechanisms that enhance the performances of the materials including self-healing, reprocessing, and reprogramming. The different dynamic chemistries and their mechanisms on the enhanced functions of the materials are compared and discussed, where three summary tables are presented: A library of dynamic bonds and the resulting characteristics of the materials. Finally, a critical outline of the unresolved issues and future perspectives on the emerging developments is provided.

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.

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.

Printed aerogels: chemistry, processing, and applications.

As an extraordinarily lightweight and porous functional nanomaterial family, aerogels have attracted considerable interest in academia and industry in recent decades. Despite the application scopes, the modest mechanical durability of aerogels makes their processing and operation challenging, in particular, for situations demanding intricate physical structures. "Bottom-up" additive manufacturing technology has the potential to address this drawback. Indeed, since the first report of 3D printed aerogels in 2015, a new interdisciplinary research area combining aerogel and printing technology has emerged to push the boundaries of structure and performance, further broadening their application scope. This review summarizes the state-of-the-art of printed aerogels and presents a comprehensive view of their developments in the past 5 years, and highlights the key near- and mid-term challenges.

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.

Hybrid Transition Metal Dichalcogenide/Graphene Microspheres for Hydrogen Evolution Reaction.

A peculiar 3D graphene-based architecture, i.e., partial reduced-Graphene Oxide Aerogel Microspheres (prGOAM), having a dandelion-like morphology with divergent microchannels to implement innovative electrocatalysts for the hydrogen evolution reaction (HER) is investigated in this paper. prGOAM was used as a scaffold to incorporate exfoliated transition metals dichalcogenide (TMDC) nanosheets, and the final hybrid materials have been tested for HER and photo-enhanced HER. The aim was to create a hybrid material where electronic contacts among the two pristine materials are established in a 3D architecture, which might increase the final HER activity while maintaining accessible the TMDC catalytic sites. The adopted bottom-up approach, based on combining electrospraying with freeze-casting techniques, successfully provides a route to prepare TMDC/prGOAM hybrid systems where the dandelion-like morphology is retained. Interestingly, the microspherical morphology is also maintained in the tested electrode and after the electrocatalytic experiments, as demonstrated by scanning electron microscopy images. Comparing the HER activity of the TMDC/prGOAM hybrid systems with that of TMDC/partially reduced-Graphene Oxide (prGO) and TMDC/Vulcan was evidenced in the role of the divergent microchannels present in the 3D architecture. HER photoelectron catalytic (PEC) tests have been carried out and demonstrated an interesting increase in HER performance.

High Silica Content Graphene/Natural Rubber Composites Prepared by a Wet Compounding and Latex Mixing Process.

The reduced graphene oxide (rGO) modified natural rubber composite (NR) filled with high contents of silica was prepared by a wet compounding and latex mixing process using a novel interface modifier cystamine dihydrochloride (CDHC) with coagulation ability. CDHC acts as a coagulation agent through electrostatic interaction with rGO, SiO2, and latex rubber particles during the latex-based preparation process, while in the obtained silica/graphene/natural rubber composites, CDHC acts as an interface modifier. Compared with the composites prepared by the conventional mechanical mixing method, the dispersion of both rGO and SiO2 in the composites made by a wet compounding and latex mixing process is improved. As a result, the obtained silica/graphene/natural rubber composite prepared by this new method has good comprehensive properties. A Dynamic Mechanical Test suggests that the tan δ values of the composites at 60 °C decrease, indicating a low rolling resistance with increasing the graphene content at a low strain, but it increases at a higher strain. This unique feature for this material provides an advantage in the rubber tire application.

Terahertz Optics of Materials with Spatially Harmonically Distributed Refractive Index.

The electromagnetic properties of structures with spatially periodic distributed graded refractive index were investigated in the terahertz frequency range. The band structure and electromagnetic response of material with harmonically distributed refractive index were calculated and analyzed. The analytical expressions for frequencies of the first and second bandgap are derived. 3D printed gyroid based architectures were proven to be harmonically graded refractive index structures with designed bandgaps in THz frequency ranges. The transmission coefficient of thermoplastic polyurethane-based samples were experimentally measured in the frequency range 100-500 GHz and compared with theoretical results. Due to losses in the real world produced samples, the predicted response is significantly dumped in the terahertz range and only traces of band gaps are experimentally observed. This funding paves the way toward a new generation of 3D printed THz components for gradient-index optics applications.

The Transferability and Design of Commercial Printer Settings in PLA/PBAT Fused Filament Fabrication.

In many fused filament fabrication (FFF) processes, commercial printers are used, but rarely are printer settings transferred from one commercial printer to the other to give similar final tensile part performance. Here, we report such translation going from the Felix 3.0 to Prusa i3 MK3 printer by adjusting the flow rate and overlap of strands, utilizing an in-house developed blend of polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT). We perform a sensitivity analysis for the Prusa printer, covering variations in nozzle temperature, nozzle diameter, layer thickness, and printing speed (Tnozzle, dnozzle, LT, and vprint), aiming at minimizing anisotropy and improving interlayer bonding. Higher mass, larger width, and thickness are obtained with larger dnozzle, lower vprint, higher LT, and higher Tnozzle. A higher vprint results in less tensile strain at break, but it remains at a high strain value for samples printed with dnozzle equal to 0.5 mm. vprint has no significant effect on the tensile modulus and tensile and impact strength of the samples. If LT is fixed, an increased dnozzle is beneficial for the tensile strength, ductility, and impact strength of the printed sample due to better bonding from a wider raster structure, while an increased LT leads to deterioration of mechanical properties. If the ratio dnozzle/LT is greater than 2, a good tensile performance is obtained. An improved Tnozzle leads to a sufficient flow of material, contributing to the performance of the printed device. The considerations brought forward result in a deeper understanding of the FFF process and offer guidance about parameter selection. The optimal dnozzle/vprint/LT/Tnozzle combination is 0.5 mm/120 mm s-1/0.15 mm/230 °C.