Enhancing the Humidity Resistance of Triboelectric Nanogenerators: A Review.

Triboelectric nanogenerators (TENGs) are sustainable energy resources for powering electronic devices from miniature to large-scale applications. However, their output performance and stability can deteriorate significantly when TENGs are exposed to moisture or humidity caused by the ambient environment or human physiological activities. This review provides an overview of the recent research advancements in enhancing the humidity resistance of TENGs. Various approaches have been reviewed including encapsulation techniques, surface modification of triboelectric materials to augment hydrophobicity or superhydrophobicity, the creation of fibrous architectures for effective moisture dissipation, leveraging water assistance for TENG performance enhancement, and other strategies like charge excitation. These research efforts contribute to the improvement of environmental adaptability and lead to expanded practical TENG applications both as energy harvesters and self-powered sensors. The efficacy of these strategies and future challenges are also discussed to facilitate the continued development of resilient TENGs in high humidity environments.

Biomimetic Multifunctional Graphene-Based Coating for Thermal Management, Solar De-Icing, and Fire Safety: Inspired from the Antireflection Nanostructure of Compound Eyes.

Due to the ubiquitous and inexhaustible solar source, photothermal materials have gained considerable attention for their potential in heating and de-icing. Nevertheless, traditional photothermal materials, exemplified by graphene, frequently encounter challenges emanating from their elevated reflectance. Inspired by ocular structures, this study uses the Fresnel equation to enhance the photo-thermal conversion efficiency of graphene by introducing a polydimethylsiloxane (PDMS)/silicon dioxide (SiO2) coating, which reduces the light reflectance (≈20%) through destructive interference. The designed coating achieves an equilibrium temperature of ≈77 °C at one sun and a quick de-icing in ≈65 s, all with a thickness of 5 µm. Simulations demonstrate that applying this coating to high-rise buildings results in energy savings of ≈31% in winter heating. Furthermore, the combination of PDMS/SiO2 and graphene confers a notable enhancement in thermal stability through a synergistic flame-retardant mechanism, effectively safeguarding polyurethane against high temperatures and conflagrations, leading to marked reduction of 58% and 28% in heat release rate and total heat release. This innovative design enhances the photo-thermal conversion, de-icing function, and flame retardancy of graphene, thereby advancing its applications in outdoor equipment, high-rise buildings, and aerospace vessels.

Supramolecular Complexation Reinforced Polymer Frustrated Packing: Controllable Dual Porosity for Improved Permselectivity of Coordination Nanocage Mixed Matrix Membranes.

The developments of mixed matrix membranes (MMMs) are severely hindered by the complex inter-phase interaction and the resulting poor utilization of inorganics' microporosity. Herein, a dual porosity framework is constructed in MMMs to enhance the accessibility of inorganics' microporosity to external gas molecules for the effective application of microporosity for gas separation. Nanocomposite organogels are first prepared from the supramolecular complexation of rigid polymers and 2 nm microporous coordination nanocages (CNCs). The network structures can be maintained with microporous features after solvent removal originated from the rigid nature of polymers, and the strong coordination and hydrogen bond between the two components. Moreover, the strong supramolecular attraction reinforces the frustrated packing of the rigid polymers on CNC surface, leading to polymer networks' extrinsic pores and the interconnection of CNCs' micro-cavities for the fast gas transportation. The gas permeabilities of the MMMs are 869 times for H2 and 1099 times for CO2 higher than those of pure polymers. The open metal sites from nanocage also contribute to the enhanced gas selectivity and the overall performance surpasses 2008 H2/CO2 Robeson upper bound. The supramolecular complexation reinforced packing frustration strategy offers a simple and practical solution to achieve improved gas permselectivity in MMMs.

Flexible 3D Force Sensor Based on Polymer Nanocomposite for Soft Robotics and Medical Applications.

The three-dimensional (3D) force sensor has become essential in industrial and medical applications. The existing conventional 3D force sensors quantify the three-direction force components at a point of interest or extended contact area. However, they are typically made of rigid, complex structures and expensive materials, making them hard to implement in different soft or fixable industrial and medical applications. In this work, a new flexible 3D force sensor based on polymer nanocomposite (PNC) sensing elements was proposed and tested for its sensitivity to forces in the 3D space. Multi-walled carbon nanotube/polyvinylidene fluoride (MWCNT/PVDF) sensing element films were fabricated using the spray coating technique. The MWCNTs play an essential role in strain sensitivity in the sensing elements. They have been utilized for internal strain measurements of the fixable 3D force sensor's structure in response to 3D forces. The MWCNT/PVDF was selected for its high sensitivity and capability to measure high and low-frequency forces. Four sensing elements were distributed into a cross-beam structure configuration, the most typically used solid 3D force sensor. Then, the sensing elements were inserted between two silicone rubber layers to enhance the sensor's flexibility. The developed sensor was tested under different static and dynamic loading scenarios and exhibited excellent sensitivity and ability to distinguish between tension and compression force directions. The proposed sensor can be implemented in vast applications, including soft robotics and prostheses' internal forces of patients with limb amputations.

Supramolecular Assembly and Microscopic Dynamics Modulation of Nanoscale Inorganic Cryptand and Polymer Complex for Versatile Design of Flexible Single-Ion Conductors.

The popular design of solid-state electrolytes (SSEs) from the chain relaxation of polymers faces the trade-offs among ion conductivity, stability, and processability. Herein, 2 nm inorganic cryptand molecules with the capability to carry different types of cations, including Ag+, Na+, K+, and Ca2+, are complexed with cationic polymers via ionic interaction, respectively, and the hybrid materials further phase separate into lamellar or hexagonal columnar structures. The successful establishment of ordered structures with ion channels from the packing of inorganic cryptands confers SSEs' excellent ionic conductivity to versatile types of cations. Meanwhile, suggested from the combination of broad dielectric spectroscopy, rheology, and thermal analysis, the fast chain relaxation can activate the dynamics of inorganic cryptand molecules and facilitate the ion hopping process in ion channels. The supramolecular interaction in the complex enables the highly flexible physical appearance for defect-free contact with electrodes as well as cost-effective processability and recyclability.

Linking Interfacial Bonding and Thermal Conductivity in Molecularly-Confined Polymer-Glass Nanocomposites with Ultra-High Interfacial Density.

Thermal transport in polymer nanocomposites becomes dependent on the interfacial thermal conductance due to the ultra-high density of the internal interfaces when the polymer and filler domains are intimately mixed at the nanoscale. However, there is a lack of experimental measurements that can link the thermal conductance across the interfaces to the chemistry and bonding between the polymer molecules and the glass surface. Characterizing the thermal properties of amorphous composites are a particular challenge as their low intrinsic thermal conductivity leads to poor measurement sensitivity of the interfacial thermal conductance. To address this issue here, polymers are confined in porous organosilicates with high interfacial densities, stable composite structure, and varying surface chemistries. The thermal conductivities and fracture energies of the composites are measured with frequency dependent time-domain thermoreflectance (TDTR) and thin-film fracture testing, respectively. Effective medium theory (EMT) along with finite element analysis (FEA) is then used to uniquely extract the thermal boundary conductance (TBC) from the measured thermal conductivity of the composites. Changes in TBC are then linked to the hydrogen bonding between the polymer and organosilicate as quantified by Fourier-transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy. This platform for analysis is a new paradigm in the experimental investigation of heat flow across constituent domains.

Emerging synthesis and characterization techniques for hybrid polymer nanocomposites.

Metallic nanoparticles and carbon nanotubes are two of the most promising nanomaterials, due to their distinctive properties occurring from spatial confinement of electron-hole pairs. The unique combination of metallic nanoparticles and carbon nanotubes (CNTs) in a polymer matrix offers unparalleled advantages, making them highly desirable in various fields. Advanced methods and techniques for synthesizing and characterizing hybrid metal-CNT-polymer nanocomposites have undergone significant progress in recent years, paving their integration into various fields, including aerospace, electronics, energy, water treatment and environmental remediation. These advances have allowed better understanding of nanocomposite properties and imparted ability to tune specific properties through size, shape, and distribution control of the nanofillers within the matrix material or by altering filler properties through functionalization. This study aims to critically judge the emerging tools, techniques and methods used in polymer nanocomposites with specific focus on metal-CNT based hybrid polymer nanocomposites, and suggest new avenues for research in the field. Furthermore, by examining the mechanisms affecting the performance of these composites, we can understand how the inclusion of fillers alters the microstructure and overall behavior of the material. Ultimately, this knowledge could lay the foundation for the development of novel nanocomposites with tailored properties and enhanced performance in a plethora of applications.

Spontaneous Transformation of Biomedical Polymeric Silver Salt into a Nanocomposite: Physical-Chemical and Antimicrobial Properties Dramatically Depend on the Initial Preparation State.

An antimicrobial polyacrylic silver salt (freshly prepared, stored for one year and model-aged) was studied by physical-chemical techniques for nanoparticle detection. In all cases, this salt represents a composite of radical-enriched macromolecules and silver(0) nanoparticles. As time passed, the initial small spherical nanoparticles were converted into larger non-spherical silver nanoparticles. The initial highly water-soluble antimicrobial solid nanocomposite almost loses its solubility in water and cannot be used as an antimicrobial agent. Unlike insoluble solid silver polyacrylate, its freshly prepared aqueous solution retains a liquid-phase consistency after one year as well as pronounced antimicrobial properties. The mechanism of these spontaneous and model-simulated processes was proposed. These results have attracted attention for officinal biomedicinal silver salts as complex radical-enriched nanocomposite substances; they also indicate contrasting effects of silver polymeric salt storing in solid and solution forms that dramatically influence antimicrobial activity.

The Role of Phase Migration of Carbon Nanotubes in Melt-Mixed PVDF/PE Polymer Blends for High Conductivity and EMI Shielding Applications.

In this work, the effects of blend ratio and mixing time on the migration of multi-walled carbon nanotubes (MWCNTs) within poly(vinylidene fluoride) (PVDF)/polyethylene (PE) blends are studied. A novel two-step mixing approach was used to pre-localize MWCNTs within the PE phase, and subsequently allow them to migrate into the thermodynamically favored PVDF phase. Light microscopy images confirm that MWCNTs migrate from PE to PVDF, and transmission electron microscopy (TEM) images show individual MWCNTs migrating fully into PVDF, while agglomerates remained trapped at the PVDF/PE interface. PVDF:PE 50:50 and 20:80 polymer blend nanocomposites with 2 vol% MWCNTs exhibit exceptional electromagnetic interference shielding effectiveness (EMI SE) at 10 min of mixing (13 and 16 dB, respectively-at a thickness of 0.45 mm), when compared to 30 s of mixing (11 and 12 dB, respectively), suggesting the formation of more interconnected MWCNT networks over time. TEM images show that these improved microstructures are concentrated on the PE side of the PVDF/PE interface. A modified version of the "Slim-Fast-Mechanism" is proposed to explain the migration behavior of MWCNTs within the PVDF/PE blend. In this theory, MWCNTs approaching perpendicular to the interface penetrate the PVDF/PE interface, while those approaching in parallel or as MWCNT agglomerates remain trapped. Trapped MWCNTs act as barriers to additional MWCNTs, regardless of geometry. This mechanism is verified via TEM and scanning electron microscopy and suggests the feasibility of localizing MWCNTs at the interface of PVDF/PE blends.

Improved thermal stability of antireflective moth-eye topography imprinted on PMMA/TiO2surface nanocomposites.

The thermal stability of antireflective moth-eye topographical features fabricated by nanoimprint lithography on poly (methyl methacrylate) (PMMA) incorporating TiO2nanoparticles is explored. The effect of nanoparticle load on the relaxation dynamics of the moth-eye nanostructure is evaluated via grazing incidence small angle x-ray scattering measurements byin situmonitoring the structural decay of the nanopatterns upon thermal annealing. It is demonstrated that the incorporation of TiO2nanoparticles to the imprinted surface nanocomposite films delays greatly the pattern relaxation which, in turn, enhances the stability of the patterned topography even at temperatures well above the polymer glass transition (Tg). The improved thermal behavior of the antireflective films will significantly enhance their functionality and performance in light-trapping applications where temperatures typically rise, such as solar devices or solar glass panels.

Development of novel TPI/HDPE/CNTs ternary hybrid shape memory nanocomposites.

In order to make up for the defects of trans-1,4-polyisoprene (TPI) shape memory polymer, TPI/high density polyethylene (HDPE) hybrid shape memory matrix was prepared from the perspective of matrix composition. The carbon nanotubes (CNTs) with excellent mechanical properties were introduced into the hybrid shape memory matrix. Due to the difference of the inherent properties and geometry of nano-fillers, the change of the content of nano-fillers directly affects the bonding state within the composites. Therefore, it is very important to choose the appropriate content. In order to give full play to the potential of thermodynamics of nano-filler, the TPI/HDPE/CNTs ternary hybrid shape memory nanocomposites were prepared by mechanical melt blending technology combined with dynamic vulcanization and hot-pressing forming technology. The addition of CNTs promotes the formation of the crystal structure of TPI and HDPE, and facilitates the energy transfer between different interface, which greatly improves the thermal conductivity and mechanical properties of the nanocomposites at the same time. The effect of the changes of filler content on the thermodynamic properties of the composite materials were revealed by series of tests. The results show that the CNTs act as nucleating agents in the crystallization region of TPI and HDPE. However, the excessive addition of CNTs can inhibit the formation of HDPE crystal structure. Meanwhile, the crystallinity of nanocomposites is also an important factor affecting its thermal conductivity. The specimens with the CNTs content of 0.5 wt% have excellent tensile resistance and cyclic recovery ability, and it can improve the shape recovery properties. Therefore, the nanocomposite with the CNTs content of 0.5 wt% has the best thermodynamic and shape memory properties.

Tactile and Thermal Sensors Built from Carbon-Polymer Nanocomposites-A Critical Review.

This paper provides a critical review of tactile and thermal sensors which are built from carbon nanomaterial-filled polymer composites (CNPCs). To make the review more comprehensive and systematic, the sensors are viewed as a system, and a general knowledge architecture for a system called function-context-behavior-principle-state-structure (FCBPSS) is employed to classify information as well as knowledge related to CNPC sensors. FCBPSS contains six basic concepts, namely, F: function, C: context, B: behavior, P: principle, and SS: state and structure. As such, the principle that explains why such composites can work as temperature and pressure sensors, various structures of the CNPC sensor, which realize the principle, and the behavior and performance of CNPC sensors are discussed in this review. This review also discusses the fabrication of the CNPC sensor. Based on the critical review and analysis, the future directions of research on the CNPC sensor are discussed; in particular, the need to have a network of CNPC sensors that can be installed on curved bodies such as those of robots is elaborated.

Elucidating the Role of Interfacial Hydrogen Bonds on Glass Transition Temperature Change in a Poly(Vinyl Alcohol)/SiO2 Polymer-Nanocomposite by Noncovalent Interaction Characterization and Atomistic Molecular Dynamics Simulations.

A thorough experimental investigation of polymer-glass transition temperature (Tg ) is performed on poly(vinyl alcohol) (PVA) and fumed silica nanoparticle (SiNP) composite. This is done together with atomistic molecular dynamics simulations of PVA systems in contact with bare and fully hydroxylated silica. Experimentally, PVA-SiNP composites are prepared by simple solution casting from aqueous solutions followed by its characterization using Fourier-transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), and dynamic scanning calorimetry (DSC). Both theoretical and experimentally deduced Tg are correlated with the presence of hydrogen bonding interactions involving OH functionality present on the surface of SiNP and along PVA polymer backbone. Further deconvolution of FTIR data show that inter-molecular hydrogen bonding present between PVA and SiNP surface is directly responsible for the increase in Tg . SiNP filler and PVA matrix ratio is also optimized for a desired Tg increase. An optimal loading of SiNP exists, in order to yield the maximum Tg increase arising from the competition between hydrogen bonding and crowding effect of SiNP.

Graphene/polymer nanocomposite degradation by ultraviolet light: The effects of graphene nanofillers and their potential for release.

The ultraviolet (UV)-induced degradation of graphene/polymer nanocomposites was investigated in this study. Specifically, the effect of few-layer graphene nanofillers on the degradation of a thermoplastic polyurethane (TPU) and the release potential of graphene from the degraded nanocomposite surfaces were assessed. Graphene/TPU (G/TPU) nanocomposites and neat TPU were UV-exposed under both dry and humid conditions in the NIST SPHERE, a precisely controlled, high intensity UV-weathering device. Neat TPU and G/TPU were characterized over the time course of UV exposure using color measurements and infrared spectroscopy, for appearance and chemical changes, respectively. Changes in thickness and surface morphology were obtained with scanning electron microscopy. A new fluorescence quenching measurement approach was developed to identify graphene sheets at the nanocomposite surface, which was supported by contact angle measurements. The potential for graphene release from the nanocomposite surface was evaluated using a tape-lift method followed by microscopy of any particles present on the tape. The findings suggest that graphene improves the service life of TPU with respect to UV exposure, but that graphene becomes exposed at the nanocomposite surface over time, which may potentially lead to its release when exposed to small mechanical forces or upon contact with other materials.

Process Parameters for FFF 3D-Printed Conductors for Applications in Sensors.

With recent developments in additive manufacturing (AM), new possibilities for fabricating smart structures have emerged. Recently, single-process fused-filament fabrication (FFF) sensors for dynamic mechanical quantities have been presented. Sensors measuring dynamic mechanical quantities, like strain, force, and acceleration, typically require conductive filaments with a relatively high electrical resistivity. For fully embedded sensors in single-process FFF dynamic structures, the connecting electrical wires also need to be printed. In contrast to the sensors, the connecting electrical wires have to have a relatively low resistivity, which is limited by the availability of highly conductive FFF materials and FFF process conditions. This study looks at the Electrifi filament for applications in printed electrical conductors. The effect of the printing-process parameters on the electrical performance is thoroughly investigated (six parameters, >40 parameter values, >200 conductive samples) to find the highest conductivity of the printed conductors. In addition, conductor embedding and post-printing heating of the conductive material are researched. The experimental results helped us to understand the mechanisms of the conductive network's formation and its degradation. With the insight gained, the optimal printing strategy resulted in a resistivity that was approx. 40% lower than the nominal value of the filament. With a new insight into the electrical behavior of the conductive material, process optimizations and new design strategies can be implemented for the single-process FFF of functional smart structures.

Engineered Zero-Dimensional Fullerene/Carbon Dots-Polymer Based Nanocomposite Membranes for Wastewater Treatment.

With the rapid growth of industrialization, diverse pollutants produced as by-products are emitted to the air-water ecosystem, and toxic contamination of water is one of the most hazardous environmental issues. Various forms of carbon have been used for adsorption, electrochemical, and ion-exchange membrane filtration to separation processes for water treatment. The utilization of carbon materials has gained tremendous attention as they have exceptional properties such as chemical, mechanical, thermal, antibacterial activities, along with reinforcement capability and high thermal stability, that helps to maintain the ecological balance. Recently, engineered nano-carbon incorporated with polymer as a composite membrane has been spotlighted as a new and effective mode for water treatment. In particular, the properties of zero-dimensional (0D) carbon forms (fullerenes and carbon dots) have encouraged researchers to explore them in the field of wastewater treatment through membrane technologies as they are biocompatible, which is the ultimate requirement to ensure the safety of drinking water. Thus, the purpose of this review is to highlight and summarize current advances in the field of water purification/treatment using 0D carbon-polymer-based nanocomposite membranes. Particular emphasis is placed on the development of 0D carbon forms embedded into a variety of polymer membranes and their influence on the improved performance of the resulting membranes. Current challenges and opportunities for future research are discussed.

Stiffness-Changing of Polymer Nanocomposites with Cellulose Nanocrystals and Polymeric Dispersant.

Bio-inspired, water-responsive, mechanically adaptive nanocomposites are reported based on cellulose nanocrystals (CNCs), poly(ethylene oxide-co-epichlorohydrin) (EO-EPI), and a small amount of poly(vinyl alcohol) (PVA), which is added to aid the dispersion of the CNCs. In the dry state, the CNCs form a reinforcing network within the polymer matrix, and the substantial stiffness increase relative to the neat polymer is thought to be the result of hydrogen-bonding interactions between the nanocrystals. Exposure to water, however, causes a large stiffness reduction, due to competitive hydrogen bonding of water molecules and the CNCs. It is shown here that the addition of PVA to the EO-EPI/CNC nanocomposite increases the modulus difference between the dry and the wet state by a factor of up to four compared to the nanocomposites without the PVA. The main reason is that the PVA leads to a substantial increase of the stiffness in the dry state; for example, the storage modulus E ' increased from 2.7 MPa (neat EO-EPI) to 50 MPa upon introduction of 10% CNCs, and to 200 MPa when additionally 5% of PVA was added. By contrast, the incorporation of PVA only led to moderate increases of the equilibrium water swelling and the E ' in the wet state.

Low fouling electrochemical sensing in complex biological media by using the ionic liquid-doped conducting polymer PEDOT: application to voltammetric determination of dopamine.

An electrochemical sensor that can resist biofouling even when operated in complex biological medium is developed for the determination of dopamine. It is based on the use of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) that is doped with the water insoluble ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A glassy carbon electrode modified with PEDOT/IL is shown to enable accurate determination of dopamine, as a model analyte in the presence of high concentrations of proteins, and resist biological fouling even in native serum. It exhibited a low limit of detection of 33 nM for the detection of dopamine, with a wide linear range from 0.2 to 328 µM (at 0.2 V vs. saturated calomel electrode). The PEDOT/IL modified glassy carbon electrode has a porous microstructure, high electrical conductivity and good stability. The sensor can be used to quantify dopamine in human urine samples with satisfying accuracy. Graphical abstract An antifouling electrochemical sensor capable of detecting target in complex biological samples was developed based on the use of a conducting polymer (PEDOT) that was doped with a water insoluble ionic liquid.

Mannose functionalized plain and endosomolytic nanocomposite(s)-based approach for the induction of effective antitumor immune response in C57BL/6 mice melanoma model.

The goal of present study to assess the antigen specific immunopotentiation effect of mannose functionalized endosomolytic and conventional nanocomposite(s) based combination approach using C57BL/6 mice melanoma model. Endosomolytic and conventional nanocomposite(s) were prepared by double emulsification method. The optimized formulation was extensively characterized for average particle size, zeta potential and PDI of nanocomposite(s) which were measured in range of ≈200 nm, 0.111 ± 0.024, -23.4 ± 2.0 mV, respectively. pH-dependent morphological changes in the surface of MRPRPNs and PRPNs were analyzed by using surface electron microscopy at different time intervals. The cellular uptake assessment of developed formulations were followed by using RAW 264.7 macrophage cell lines. Results revealed that after immunizing B16F10 melanoma cells implanted C57BL/6 mice with combination [endosomolytic and conventional nanocomposite(s)] of nanocomposite(s), a significant increase in the interleukins level i.e. IL-2, IFN-ϒ, IL-12 and IL-6 and OVA Ag(s) specific antibody responses were recorded. Consequently, a strong immunological response was elicited with specific polarization contributing to humoral and activation of CD8+ to cellular responses. Finding of histological examination also support the potential of therapeutic outcome. The present approach based on mannose surface functionalization for targeting to antigen presenting cells and pH-dependent prompt endosomal release and escape can be a promising system for efficient cancer immunotherapy.

Three-Dimensional Printing of Cytocompatible, Thermally Conductive Hexagonal Boron Nitride Nanocomposites.

Hexagonal boron nitride (hBN) is a thermally conductive yet electrically insulating two-dimensional layered nanomaterial that has attracted significant attention as a dielectric for high-performance electronics in addition to playing a central role in thermal management applications. Here, we report a high-content hBN-polymer nanocomposite ink, which can be 3D printed to form mechanically robust, self-supporting constructs. In particular, hBN is dispersed in poly(lactic- co-glycolic acid) and 3D printed at room temperature through an extrusion process to form complex architectures. These constructs can be 3D printed with a composition of up to 60% vol hBN (solids content) while maintaining high mechanical flexibility and stretchability. The presence of hBN within the matrix results in enhanced thermal conductivity (up to 2.1 W K-1 m-1) directly after 3D printing with minimal postprocessing steps, suggesting utility in thermal management applications. Furthermore, the constructs show high levels of cytocompatibility, making them suitable for use in the field of printed bioelectronics.