Wearable and Recyclable Water-Toleration Sensor Derived from Lipoic Acid.

Flexible wearable sensors recently have made significant progress in human motion detection and health monitoring. However, most sensors still face challenges in terms of single detection targets, single application environments, and non-recyclability. Lipoic acid (LA) shows a great application prospect in soft materials due to its unique properties. Herein, ionic conducting elastomers (ICEs) based on polymerizable deep eutectic solvents consisting of LA and choline chloride are prepared. In addition to the good mechanical strength, high transparency, ionic conductivity, and self-healing efficiency, the ICEs exhibit swelling-strengthening behavior and enhanced adhesion strength in underwater environments due to the moisture-induced association of poly(LA) hydrophobic chains, thus making it possible for underwater sensing applications, such as underwater communication. As a strain sensor, it exhibits highly sensitive strain response with repeatability and durability, enabling the monitoring of both large and fine human motions, including joint movements, facial expressions, and pulse waves. Furthermore, due to the enhancement of ion mobility at higher temperatures, it also possesses excellent temperature-sensing performance. Notably, the ICEs can be fully recycled and reused as a new strain/temperature sensor through heating. This study provides a novel strategy for enhancing the mechanical strength of poly(LA) and the fabrication of multifunctional sensors.

High energy capability in poly(vinylidene fluoride-co-chlorotrifluoroethylene) nanocomposite incorporated with Ag@polyaniline@covalent organic framework core-shell nanowire.

The development of polymer film with large electrical displacement is essential for the applications of lightweight and compact energy storage. The dielectric diversity at interface of polymer composite should be addressed to realize the film capacitor with high energy density and dielectric reliability. In this work, poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-CTFE)) nanocomposite was incorporated by core-shell nanowire with covalent organic framework (COF) outer coating to alleviate the dielectric mismatch at interface. After the preparation of Ag nanowire through polyol reduction, polyaniline (PANI) and COF layers were sequentially deposited to construct core-shell Ag@polyaniline@covalent organic framework (Ag@PANI@COF) nanowire. According to the unique core-shell architecture, the COF framework is utilized to suppress the remanent polarization while high electrical displacement is preserved by the center Ag nanowire. The maximum energy density of 25.0 J/cm3 at 425 MV/m is obtained in 0.1 wt% stretched Ag@PANI@COF/P(VDF-CTFE) nanocomposite. The presence of core-shell nanowire depresses the distribution distortion of electric field and the diffusion of charge carriers under high field. This work demonstrates an effective method to develop the polymer film with large electrical displacement, and sheds a light on insightful exploration of interfacial polarized mechanism in polymer dielectric composite.

Efficient, Robust, and Flame-Retardant Electrothermal Coatings Based on a Polyhedral Oligomeric Silsesquioxane-Functionalized Graphene/Multiwalled Carbon Nanotube Hybrid with a Dually Cross-Linking Structure.

Graphene electrothermal coatings have attracted considerable attention in recent years due to their important application prospects in a broad range of areas. So far, lots of strategies have been explored for producing them. However, these strategies usually involve a complicated process with sophisticated conditions, limiting their scalable applications. Herein, we demonstrate a facile strategy for preparing efficient, robust, and flame-retardant electrothermal coatings from liquid-phase exfoliated graphene, by combining with multiwalled carbon nanotubes (MWCNTs) and polyhedral oligomeric silsesquioxane (POSS) nanoparticles. This relies on the use of a hyperbranched polyethylene copolymer that simultaneously bears UV-reactive moieties and POSS terminal groups. As a stabilizer, the copolymer can effectively promote the exfoliation of both graphite and MWCNTs in common organic solvents under sonication, rendering the POSS-functionalized graphene and MWCNTs well dispersible in the solvent. From their dispersions, POSS-functionalized graphene/MWCNT hybrid electrothermal coatings have been successfully prepared simply by vacuum filtration and UV irradiation under mild conditions. It has been confirmed that a dually cross-linking structure can be formed in the hybrid system. This significantly improves the thermal resistance of resultant coatings, which remain exhibiting a stable work state even at a temperature high as 280 °C without the occurrence of flammation. Meanwhile, this also endows them with excellent electrothermal performance and service stability. At a relatively low voltage, 15 V, the steady temperature can reach 188.4 °C, with a response time < 30 s; after being alternately folded for 2700 cycles or scraped 200 times, the coating still maintains a stable state. In particular, the process involved is relatively simple with mild conditions. With these features, the coatings obtained herein may find their important applications in the area of wearable devices and household heating systems.

One-pot synthesis of hexafluorobutyl acrylate hyperbranched copolymer for graphene/poly(vinylidenefluoride-trifluoroethylene- chlorofluoroethylene) dielectric composite.

Dielectric polymer film capacitor is rapidly emerging as next-generation energy storage for advanced engineering applications because of its lightweight, low cost, and processability. Further increasing energy density of polymer film with high charge-discharge efficiency is prevalent research spotlight. The filler/polymer composite with compatible interface is proved as an effective strategy to improve the energy storage capability of dielectric film. In this work, we designed hyperbranched hexafluorobutyl acrylate copolymer as miscible interface in graphene/fluoropolymer dielectric composite. A facile one-pot method was adopted to synthesize hyperbranched polyethylene grafted hexafluorobutyl acrylate (HBPE-g-HFBA) copolymer, which was adsorbed on surface of nanosheets by non-covalent interaction during exfoliation of natural graphite. The graphene/poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) composite was prepared by solution casting. The interfacial polarization is enhanced with the improved compatibility of composite that is due to the chemical similarity between hexafluorobutyl acrylate segments and fluoropolymer matrix. The energy density of 0.1 wt% nanocomposite achieves 5.0 J cm-3with charge-discharge efficiency of 78.1% at 250 MV m-1. This work provides an optional route for non-covalent functionalization of graphene and the development of flexible polymer film capacitor with large energy storage capability.

Crystallinity and photocatalytic properties of BiVO4/halloysite nanotubes hybrid catalysts for sunlight-driven decomposition of dyes from aqueous solution.

The BiVO4/HNTs hybrid photocatalysts were synthesized by liquid phase precipitation using natural halloysite nanotubes (HNTs) as supporter and Bi(NO3)·5H2O as resource of Bi. XRD, scanning electron microscopy (SEM), transmission electron microscopy, HRTEM, x-ray photo electron spectroscopy and UV-Vis DRS were used to characterize the samples prepared at different calcination temperatures, and the effects of crystallization, Brunauer-Emmett-Teller specific surface area and morphological structure on the photoactivity were investigated. Results reveal that increasing calcination temperature can accelerate the transition of BiVO4 from tetragonal to monoclinic and also decrease the surface area of BiVO4/HNTs. The SEM results showed that BiVO4 was successfully coated on HNTs surface with ellipsoid or near rod like morphology, and the obtained BiVO4/HNTs had regular nanotube morphology. HRTEM results showed that, the regular fringe spacing of the lattice planes are about 0.474 and 0.364 nm, which is consistent with the (110) and (200) plane of the monoclinic and tetragonal BiVO4, confirming the exiting of mixed crystal structure in BiVO4/HNTs. BiVO4 with tetragonal phase (80.02%) and monoclinic phase (19.98%) mixed crystal is loaded on the surface of HNTs with calcinations at 400 °C for 2 h. The structure and Si (Al)-O bond of HNTs can be obviously changed over the calcination temperature of 400 °C. The effect of calcination temperature on photocatalytic reactivity of samples was investigated by degradation of dyes (MB, MO and RhB) under simulated solar light. And the sample calcined at 400 °C with the better mixed crystalline structure and larger specific surface area exhibits significant activity with the removal rate of MB and RhB up to 100% within 4 h. The degradation of MB follows the first order kinetic model. BiVO4/HNTs photocatalysts with the band gap of 2.34 eV has higher photocatalytic reaction rate and better sedimentation performance than Degussa P25. The photocatalytic degradation efficiency of BiVO4/HNTs for MB was no significant reduction after four times recycles.

Improved polarization and energy density in boron nitride nanosheets/poly(vinylidene fluoride-chlorotrifluoroethylene) nanocomposite with trilayered architecture regulation.

A polymer film capacitor with high energy density has attracted great attention in recent decades to fulfil the requirements of miniaturization and light weight for electronics and energy storage systems. The multi-layered nanocomposite exhibits an effective route for developing polymer film with large energy capability due to the advantage of each layer. Here, two sandwich constructions of boron nitride nanosheets (BNNSs)/poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) nanocomposite film were designed to investigate the effects of architecture regulation on energy storage performance, i.e. the nanocomposite serving as an inner layer with pristine films as outer layers, in which the nanocomposite film delivers a strongly polarized behavior and the pristine polymer provides a high breakdown strength. The BNNSs were liquid exfoliated from boron nitride bulk assisted with fluoro hyperbranched copolymer that was adsorbed on the surface of nanosheets via CH-π non-covalent interactions. The presence of fluoro segments improves the compatibility between the nanosheets and the P(VDF-CTFE) matrix. The maximum polarization of 7.9 µC cm-2 at 300 MV m-1 is achieved in the tailored sandwich film, and the discharged energy density of 9.1 J cm-3 is obtained in the current nanocomposite, which benefits from the barrier effect between adjacent layers induced by the redistribution of electric field and emerging charge traps at the interfaces. This sandwich BNNSs/P(VDF-CTFE) nanocomposite provides an insightful prospect for structural design with respect to the advanced application of the polymer film capacitor.

Efficient exfoliation of UV-curable, high-quality graphene from graphite in common low-boiling-point organic solvents with a designer hyperbranched polyethylene copolymer and their applications in electrothermal heaters.

The use of stabilizer with designer structures can effectively promote graphite exfoliation in common solvents to render functionalized graphene desirable for their various applications. Herein, a hyperbranched polyethylene copolymer, HBPE@Py@Acryl, simultaneously bearing multiple pyrene terminal groups and pendant acryloyl moieties has been successfully synthesized from ethylene with a Pd-diimine catalyst based on unique chain walking mechanism. The unique structural design of the HBPE@Py@Acryl makes it capable of effectively promote graphite exfoliation in a series of common, low-boiling-point organic solvents, e.g. CHCl3, to render stable graphene dispersions with concentrations effectively adjustable by changing feed concentrations of graphite and polymer or sonication time. Meanwhile, it can be irreversibly adsorbed on the exfoliated graphene surface based on the π-π interactions between them to concurrently render acryloyl-functionalized graphene free of structural defects, with majority (92.7%) of them having a thickness of 2-3 layers. This allows us to obtain graphene electrothermal films simply by filtration and UV irradiation, which exhibit outstanding stability in use. The action mechanism of the HBPE@Py@Acryl as stabilizer for promoting graphite exfoliation and the role of UV irradiation on improving the stability in use of resulting graphene films have been elucidated.

Enhanced interfacial polarization in poly(vinylidene fluoride-chlorotrifluoroethylene) nanocomposite with parallel boron nitride nanosheets.

The miniaturization of electronics provides an opportunity for the polymer film capacitor due to its lightweight and flexibility. In order to improve energy density and charge-discharge efficiency of the film capacitor, the development of a polymer nanocomposite is one of the effective strategies, in which the distribution of the fillers plays a key role in the enhancement of the electrical energy capability. In this work, the few-layer boron nitride nanosheets (BNNSs) was exfoliated with assistance of the fluoro hyperbranched polyethylene-graft-poly(trifluoroethyl methacrylate) (HBPE-g-PTFEMA) copolymer as stabilizer, which was adsorbed on the surface of the nanosheets via a CH-π non-covalent interaction. The morphological results confirm the lateral size of ∼0.4 µm for resultant nanosheets with the intact crystal structure. The loading of 0.5 vol% BNNSs was embedded into poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) matrix by solution casting method, and then the nanocomposite film was uniaxial stretched to achieve the orientation of nanosheets in polymer host. The dielectric constant of stretching nanocomposite with ratio of 4 at 50 mm min-1 reaches 51.1 at 100 Hz with low loss as 0.016, while the energy density of 7.0 J cm-3 at 250 MV m-1 with charge-discharge efficiency of 56% is obtained in current nanocomposite film, which is attributed to the interfacial polarization as well as parallel nanosheets blocking the growth of electrical treeing branches. This strategy of the aligned nanosheets/polymer nanocomposite establishes a simple route to construct heterogeneity in polymer films with enhanced electrical energy capability for flexible capacitors.

Poly(dimethylsiloxane)/graphene oxide composite sponge: a robust and reusable adsorbent for efficient oil/water separation.

The development of polymer sponges with large adsorption capacity, high oil/water selectivity and mechanical stability is an effective strategy for the separation of oil from oil-polluted water. The improvement in the adsorption performance for polymer sponges should not be accompanied by the sacrifice of mechanical properties and recycling stability, which are fundamental to their long-term operation in the cleanup of oil-spill accidents. In this work, we synthesized a robust and reusable sponge based on a poly(dimethylsiloxane) (PDMS) frame coated stereoscopically with graphene oxide (GO) via the amidation between PDMS and GO. The combination of the PDMS skeleton with the robust macroporous structure and GO nanosheets acting as mechanical fortifiers contributes to the nanocomposite sponge with great integrity and durability. The resultant PDMS/GO nanocomposite sponge exhibited a high compressive strength of 42.7 kPa with a strain of 60% after 50 cycles. The high adsorption capacity for various oils and organic solvents was obtained in the nanocomposite sponge, and the maximum capacity of 14.6 g g-1 was achieved for chloroform, which is ascribed to the large porosity and hydrophobicity caused by the rough PDMS skeleton covered by the GO nanosheets. Furthermore, a vacuum device with the nanocomposite sponge demonstrated effective separation for a large amount of oil/water mixture, with the maximum separation of 724 times the sponge weight during adsorption. This work provides a productive approach to develop porous polymer nanocomposites with high absorption properties and mechanical cycling stability and paves the path for the application of polymer sponges in oil pollution.

The liquid-exfoliation of graphene assisted with hyperbranched polyethylene-g-polyhedral oligomeric silsesquioxane copolymer and its thermal property in polydimethylsiloxane nanocomposite.

Thermal interface materials with high thermal conductivity are essential to transfer the redundant heat and improve the reliability of integrated circuits. Here we reported high thermal conductivity in polydimethylsiloxane (PDMS) nanocomposite incorporated with few-layer graphene, which was exfoliated in chloroform with assistance of hyperbranched polyethylene-g-polyhedral oligomeric silsesquioxane copolymer (HBPE@POSS) as the stabilizer. In order to improve the compatibility and enhance the thermal property, the HBPE@POSS copolymer was synthesized via the unique chain walking polymerization mechanism, which subsequently was applied to exfoliate natural graphite into few-layer graphene in low-boiling-point solvents. The majority of resultant nanosheets with low defects was verified with lateral dimension of ~400 nm and the thickness of ~1.6 nm, which is attributed to the presence of CH-π noncovalent interaction between graphene and HBPE@POSS copolymer. The graphene nanoplates (GNPs)/polydimethylsiloxane (PDMS) nanocomposites were prepared by solution casting, in which graphene nanofillers were dispersed uniformly in the matrix due to good compatibility between PDMS and oligomeric silsesquioxane segments adsorbed on the nanosheets. The thermal conductivity of 4.0 wt% GNPs/PDMS nanocomposite reaches 0.93 W m-1  K-1, which is 400% higher than that of pure PDMS. The PDMS nanocomposite incorporated with few-layer graphene exhibits a promising prospect in thermal interface for thermal management of electronic devices, and sheds a light on the interfacial improvement mechanism of thermal conductivity for polymer composite.

Surface characterization and degradation behavior of polyimide films induced by coupling irradiation treatment.

The degradation behavior of polyimide in extreme environments, especially under coupling treatment, directly determines the service life of several key components in spacecraft. In this research, the combined effect of a high energy electron beam (1.2 MeV), heavy tensile stress (50 MPa) and constant high temperature (150 °C) was taken into account to study the surface modification and degradation behavior of polyimide films. By analyzing surface morphology, microstructural evolution and mechanical behavior of polyimide films after coupling treatment, the results indicated that the coupling treatment led to severe breakage of chemical bonds and decrease of surface quality. Meanwhile, new chemical bonds of C-C, CH2-O and C[triple bond, length as m-dash]N formed after coupling treatment. Additionally, a high dose of electron beam during coupling experiments contributed to the formation of an oxide layer, surface defects and even volatile gases in the outer layer of the polyimide film. This was attributed to the significant scissioning of molecular chains in polyimide films and corresponding chemical reactions between free radicals and oxygen in air. Consequently, the irradiation-load-heating coupling treatment led to a remarkable drop in viscoelastic properties and mechanical performance of polyimide films.

Enhanced energy density and thermal conductivity in poly(fluorovinylidene-co-hexafluoropropylene) nanocomposites incorporated with boron nitride nanosheets exfoliated under assistance of hyperbranched polyethylene.

Polymer dielectric film with a large dielectric constant, high energy density and enhanced thermal conductivity are of significance for the development of impulse capacitors. However, the fabrication of polymer dielectrics combining high energy density and thermal conductivity is still a challenge at the moment. Here we demonstrate the facile exfoliation of hexagonal boron nitride nanosheets (BNNSs) in common organic solvents under sonication with the assistance of hyperbranched polyethylene (HBPE). The noncovalent CH-π interactions between the nanosheets and HBPE ensure the dispersion of BNNSs in organic solvents with high concentrations, because of the highly branched chain structure of HBPE. Subsequently, the resultant BNNSs with a few defects are distributed uniformly in the poly(fluorovinylidene-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films prepared via simple solution casting. The BNNS/P(VDF-HFP) nanocomposite exhibits outstanding dielectric properties, high energy density and high thermal conductivity. The dielectric constant of the 0.5 wt% nanocomposite film is 35.5 at 100 Hz with an energy density of 5.6 J cm-3 at 325 MV m-1 and a high charge-discharge efficiency of 79% due to the depression of the charge injection and chemical species ionization in a high field. Moreover, a thermal conductivity of 1.0 wt% nanocomposite film reaches 0.91 W·m-1 · K-1, which is 3.13 times higher than that of the fluoropolymer matrix. With dipole accumulation and orientation in the interfacial zone, lightweight, flexible BNNS/P(VDF-HFP) nanocomposite films with high charge-discharge performance and thermal conductivity, exhibit promising applications in relatively high-temperature electronics and energy storage devices.