Achieving a Wide-Range Linear Piezoresistive Response in Electrowritten Soft-Hard Polymer Blends via Salami-Inspired Heterostructure Design.

Flexible electronics capable of acquiring high-precision signals are in great demand for the development of the internet of things and intelligent artificial. However, it is currently a challenge to simultaneously achieve high signal linearity and sensitivity for stretchable resistive sensors over a wide strain range toward advanced application scenarios requiring high signal accuracy, e.g., sophisticated physiological signal discrimination and displacement measurement. Herein, a film strain sensor, which has an electrical and mechanical dual heterostructure, was fabricated via a direct near-field electrowriting and molecule-guided in situ growth of silver nanoparticles with different concentrations on high-modulus polystyrene domains and low-modulus styrene-butadiene copolymers with a salami-like morphology. Mechanism analyses from both theoretical and experimental investigations reveal that the salami-like heteromodulus microstructure regulates microcrack propagation routes, while the heteroconductivity changes the electron transport paths and amplifies the resistance increase during crack propagation. Therefore, the as-designed strain sensor shows a linear resistive response within ca. 70% strain with a gauge factor of 25, unveiling a simple and scalable strategy for trading off signal linearity and sensitivity over a wide strain range for the fabrication of high-performance linear strain sensors.

Thermally Conductive Magnetic Composite Phase Change Materials for Anisotropic Photo/Magnetic-to-Thermal Energy Conversion.

The distinctive thermal energy storage properties of phase change materials (PCMs) are critical for solving energy issues. However, their inherently low thermal conductivity and limited energy conversion capability impede their applications in advanced thermal energy harvesting and storage systems. Herein, we developed magnetic composite PCMs with enhanced thermal conductivity for anisotropic photothermal and magnetic-to-thermal energy conversions. The hierarchically interconnected ferroferric oxide-coated boron nitride/poly(vinyl alcohol) (BN@Fe3O4/PVA) porous scaffolds were constructed by a unidirectional freeze-casting method to enhance the directional heat transfer capability of the composite PCMs with a through-plane thermal conductivity of 1.84 W m-1 K-1 at a BN@Fe3O4 loading of 25.4 wt %. The superparamagnetic Fe3O4 nanoparticles endow the composite PCMs with unique solar absorption and magnetic response properties, and the energy conversion efficiency can be regulated by controlling the orientation of the synthesized magnetic particles in the composite PCMs. As a consequence, the resulting composite PCMs exhibit superior photo/magnetic-to-thermal energy conversion efficiency along the direction of orientation of magnetic particles. These novel findings provide an instructive guide to yield composite PCMs for efficient energy conversion.

Janus and Heteromodulus Elastomeric Fiber Mats Feature Regulable Stress Redistribution for Boosted Strain Sensing Performance.

Wearable strain sensors have huge potential for applications in healthcare, human-machine interfacing, and augmented reality systems. However, the nonlinear response of the resistance signal to strain has caused considerable difficulty and complexity in data processing and signal transformation, thus impeding their practical applications severely. Herein, we propose a simple way to achieve linear and reproducible resistive signals responding to strain in a relatively wide strain range for flexible strain sensors, which is achieved via the fabrication of Janus and heteromodulus elastomeric fiber mats with micropatterns using microimprinting second processing technology. In detail, both isotropic and anisotropic fiber mats can turn into Janus fiber mats with periodical and heteromodulus micropatterns via controlling the fiber fusion and the diffusion of local macromolecular chains of thermoplastic elastomers. The Janus heterogeneous microstructure allows for stress redistribution upon stretching, thus leading to lower strain hysteresis and improved linearity of resistive signal. Moreover, tunable sensing performance can be achieved by tailoring the size of the micropatterns on the fiber mat surface and the fiber anisotropy. The Janus mat strain sensors with high signal linearity and good reproducibility have a very low strain detection limit, enabling potential applications in human-machine interfacing and intelligent control fields if combined with a wireless communication module.

Recent Advances in Multiresponsive Flexible Sensors towards E-skin: A Delicate Design for Versatile Sensing.

Multiresponsive flexile sensors with strain, temperature, humidity, and other sensing abilities serving as real electronic skin (e-skin) have manifested great application potential in flexible electronics, artificial intelligence (AI), and Internet of Things (IoT). Although numerous flexible sensors with sole sensing function have already been reported since the concept of e-skin, that mimics the sensing features of human skin, was proposed about a decade ago, the ones with more sensing capacities as new emergences are urgently demanded. However, highly integrated and highly sensitive flexible sensors with multiresponsive functions are becoming a big thrust for the detection of human body motions, physiological signals (e.g., skin temperature, blood pressure, electrocardiograms (ECG), electromyograms (EMG), sweat, etc.) and environmental stimuli (e.g., light, magnetic field, volatile organic compounds (VOCs)), which are vital to real-time and all-round human health monitoring and management. Herein, this review summarizes the design, manufacturing, and application of multiresponsive flexible sensors and presents the future challenges of fabricating these sensors for the next-generation e-skin and wearable electronics.

Scalable Flexible Phase Change Materials with a Swollen Polymer Network Structure for Thermal Energy Storage.

3D porous structural materials are proved to be enticing candidates for the fabrication of high-performance organic phase change materials (PCMs), but the stringent fabrication process and poor processability greatly hampered their commercialization. Herein, flexible leakage-proof composite PCMs with pronounced comprehensive performance are fabricated by a scalable polymer swelling strategy without using any solvent, in which the paraffin wax (PW) segment is confined in a robust flexible 3D polymer network, giving rise to the composite PCMs with excellent form stability even at 160 °C, a high latent heat energy storage density of 133.6 J/g, and an outstanding thermal conductivity of up to ∼5.11 W/mK. More importantly, the mass production of the flexible composite phase change fiber, film, and bulk products can be achieved by adopting mature processing technologies. These resultant composite PCMs exhibit promising thermal management ability to solve the overheating problem of electronics and high-efficiency solar-thermal energy conversion capacity.

A facile strategy towards heterogeneous preparation of thermoplastic cellulose grafted polyurethane from amorphous regenerated cellulose paste.

Cellulose is an abundant feedstock with renewability and biodegradability. However, it is still challenging to manufacture natural cellulose products by environmentally friendly thermoplastic processing methods. Herein, we proposed a green approach for the heterogeneous preparation of thermoplastic cellulose grafted polyurethane (RCP-g-PU) from amorphous regenerated cellulose paste (RCP) via hydroxyl/isocyanate chemistry. First, amorphous RCP was fabricated through dissolving cellulose in sodium hydroxide aqueous solution and regenerating in polyethylene glycol, resulting in the enhancement of the accessibility of hydroxy groups in cellulose chains. Subsequently, a series of thermoplastic RCP-g-PU with the melt flow temperatures ranging from 160 °C to 226 °C were feasibly synthesized by adding hexamethylene diisocyanate into RCP without using other organic solvents. Eventually, the resultant RCP-g-PU can be directly hot-pressed into transparent films with flexibility and foldability. The reported methodology represents a sustainable route to achieve thermoplastic cellulose derivatives.

Nanofibrillar Poly(vinyl alcohol) Ionic Organohydrogels for Smart Contact Lens and Human-Interactive Sensing.

Hydrogel bioelectronics as one of the next-generation wearable and implantable electronics ensures excellent biocompatibility and softness to link the human body and electronics. However, volatile, opaque, and fragile features of hydrogels due to the sparse and microscale three-dimensional network seriously limit their practical applications. Here, we report a type of smart and robust nanofibrillar poly(vinyl alcohol) (PVA) organohydrogels fabricated via one-step physical cross-linking. The nanofibrillar network cross-linked by numerous PVA nanocrystallites enables the formation of organohydrogels with high transparency (90%), drying resistance, high toughness (3.2 MJ/m3), and tensile strength (1.4 MPa). For strain sensor application, the PVA ionic organohydrogel after soaking in NaCl solution shows excellent linear sensitivity (GF = 1.56, R2 > 0.998) owing to the homogeneous nanofibrillar PVA network. We demonstrate the potential applications of the nanofibrillar PVA-based organohydrogel in smart contact lens and emotion recognition. Such a strategy paves an effective way to fabricate strong, tough, biocompatible, and ionically conductive organohydrogels, shedding light on multifunctional sensing applications in next-generation flexible bioelectronics.

Photo-Driven Self-Healing of Arbitrary Nondestructive Damage in Polyethylene-Based Nanocomposites.

Polymer products with precise shape recovery behavior are highly desired for practical applications owing to excellent processability and mechanical properties compared with metallic or inorganic materials. Shape memory polymers (SMPs) provide a solution for this end, but the design and scalable fabrication of photothermal controllable SMPs with accurate, rapid, and repeatable recovery behaviors are still great challenges. In this work, polyurethane/sulfonated carbon nanotube (PU/S-CNT) composite particles are introduced into a cross-linked high-density polyethylene (HDPE) as a functional dispersed phase to realize photo-driven fast shape recovery in cheap polymer composite materials. It is found that microcracks can be induced by the PU/S-CNT composite particles during deformation, generating a particular microparticle in a microcrack (MC-MP) structure. The MC-MP microstructure significantly improves the photothermal conversion efficiency, thereby accelerating the photo-driven shape self-healing of arbitrary nondestructive material damage. It is also found that proper cross-linking of the matrix, HDPE, greatly improves the recovery performance of the materials. This strategy based on the MC-MP microstructure and cross-linked matrix is also instructive for designing new SMPs using other polymer materials.

Flexible Anti-Biofouling MXene/Cellulose Fibrous Membrane for Sustainable Solar-Driven Water Purification.

Solar-driven interfacial water evaporation is regarded as an effective, renewable, and environment-friendly technology for clean water production. However, biofouling caused by the nonspecific interaction between the steam generator and biofoulants generally hinders the efficient application of wastewater treatment. Herein, this work reports a facile strategy to fabricate flexible anti-biofouling fibrous photothermal membrane consisting of a MXene-coated cellulose membrane for highly efficient solar-driven water steam evaporation toward water purification applications. The as-prepared MXene/cellulose photothermal membrane exhibits light absorption efficiency as high as ∼94% in a wide solar spectrum range and a water evaporation rate up to 1.44 kg m-2 h-1 under one solar illumination. Also, the MXene/cellulose membrane shows very high antibacterial efficiency (above 99.9%) owing to the MXene coating as a highly effective bacteriostatic agent. Such a flexible, anti-biofouling, and high-efficiency photothermal membrane sheds light on practical applications in long-term wastewater treatments.

Direct modification of polyketone resin for anion exchange membrane of alkaline fuel cells.

A kind of side-chain type anion exchange membranes (AEMs) with high ionic conductivity and good comprehensive stability was prepared via direct modification of commercial engineering plastic polyketone with diamines through Paal-Knorr reaction and quaternization reaction. It was found that the amount of diamine can effectively tune the microphase morphology and properties of the prepared quaternized functionalized-polyketone anion exchange membranes (QAFPK-AEMs). The tensile strength was increased from 18.6 MPa to 38.6 MPa, and the ion exchange capacity (IEC) was increased from 1.11 mmol/g to 2.71 mmol/g depending on the amount of added diamine. The QAFPK-1-6-AEM with the IEC of 1.43 mmol/g showed the highest hydroxide conductivity of 65 mS/cm at 25 °C and 96.8 mS/cm at 80 °C. The high ionic conductivity was achieved through the establishment of effective ionic channels, and it maintained 70% of the initial ionic conductivity after the 192 h treatment in 2 mol/L KOH (aq) at 80 °C. Moreover, a peak power density of 129 mW/cm2 was achieved when the assembled single cell with QAFPK-1-6-AEM was operated at 50 °C. Thus, the prepared QAFPK-AEMs showed great potential applications for the anion exchange membrane fuel cells (AEMFCs).

Multifunctional Thermal Management Materials with Excellent Heat Dissipation and Generation Capability for Future Electronics.

Thermal management materials (TMMs) used in electronic devices are crucial for future electronics and technologies such as flexible electronics and artificial intelligence (AI) technologies. As future electronics will work in a more complicated circumstance, the overheating and overcooling problems can exist in the same electronics while the common TMMs cannot meet the demand of thermal management for future electronics. In this work, nacre-mimetic graphene-based films with super flexibility and durability (in over 10,000 tensile cycles), excellent capability to dissipate excess heat (20.84 W/(m·K) at only 16-22 µm thickness), and outstanding heating performance to generate urgent heat for electronics under extremely cold conditions are fabricated by a facile solution casting method, and the fabricated composites are proved to be superior multifunctional TMMs for the thermal management in electronic chips. In addition, the application of the paper-like films with high in-plane thermal conductivity to a flexible heat spreader and film heater is demonstrated by simulation using a finite volume method, which shows the high importance of the in-plane thermal conductivity in thermal management of electronics.

Dopamine-induced functionalization of cellulose nanocrystals with polyethylene glycol towards poly(L-lactic acid) bionanocomposites for green packaging.

Improving the physical properties of biobased polymers using bionanofillers is essential to preserve its biodegradability. This work presents a dopamine-induced functionalization of cellulose nanocrystals (CNCs) with polyethylene glycol (PEG), to enhance the crystallization, mechanical and barrier properties of poly(L-lactic acid) (PLLA) bionanocomposites. The effect of molecular weight of grafted PEG on the properties of PLLA is also studied. PEGylation of CNCs significantly enhance the crystallization of PLLA, especially for CNCs functionalized with PEG of lower molecular weight, which lead to balanced strength and ductility, and 66.4% reduction in the oxygen permeability coefficient at a low content of 0.5 wt %. Moreover, 168% improvement of ductility for PLLA can be obtained by CNCs functionalized with longer PEG chains. The surface functionalization of CNCs proposed here opens up a green avenue towards designing and fabricating fully bio-based, high-barrier and low-cost polymer nanocomposites for packaging applications.

Human Skin-Inspired Electronic Sensor Skin with Electromagnetic Interference Shielding for the Sensation and Protection of Wearable Electronics.

Increasingly serious electromagnetic radiation pollution puts higher demands on wearable devices. Electronic sensor skin capable of shielding electromagnetic radiation can provide extra protection in emerging fields such as electronic skins, robotics, and artificial intelligence, but combining the sensation and electromagnetic shielding performance together remains a great challenge. Here, inspired by the structure and functions of the human skin, a multifunctional electronic skin (M-E-skin) with both tactile sensing and electromagnetic radiation shielding functions is proposed. The tactile sensing of human skin is mimicked with irregular dermislike rough surfaces, and the electromagnetic shielding performance not available on natural skin is introduced by mimicking the ultraviolet electromagnetic radiation absorption of melanin in epidermis. The M-E-skin shows superior sensitivity (9.8 × 104 kPa-1 for the pressure range 0-0.2 kPa and 3.5 × 103 kPa-1 within 0.2-20 kPa), broad operating range (0-20 kPa), fast response and relaxation times (<62.5 ms), great pressuring-relaxing stability (10 kPa, 1000 cycles), low operating voltage (0.1 V), low power consumption (1.5 nW), and low detection limit (5 Pa). Besides, a broad range of electromagnetic wave (0.5-7.5 GHz) is shielded more than 99.66% by the M-E-skin. This work holds great potential to enlarge the application scope of current electronic skins.

Tannic acid functionalized graphene hydrogel for organic dye adsorption.

Water purification provides a feasible way to relieve the pressure of water shortage and water pollution which we are facing and adsorption is one of the most effective ways to turn polluted water into clean water. Here, we prepared graphene-tannic acid hydrogel using graphene oxide and tannic acid, a natural green reducer and adsorbent, through one-step hydrothermal method. The composition, structure, and morphology of the compounds were systematically examined. The adsorption of dyes was mainly influenced by the morphology and chemical properties of gel. The addition of tannic acid, a molecule rich in oxygen containing functional groups, changed the surface chemistry of graphene sheets and microstructures of gels, which was beneficial for contaminate adsorption. Compared with reduced graphene oxide hydrogel, the graphene-tannic acid hydrogel showed an outstanding adsorption capacity for organic dye methylene blue, more than 500 mg/g at pH 10 and the maximum adsorption capacity was up to 714 mg/g. After adsorption, ethanol and inorganic acid solution can be used as desorption agent and there was no significant adsorption capacity loss after 5 cycles.

Tailoring Crystalline Morphology by High-Efficiency Nucleating Fiber: Toward High-Performance Poly(l-lactide) Biocomposites.

In this work, a high-melting-point poly(l-lactide) fiber (hPLLA fiber) with high-efficiency nucleation activity was prepared and introduced into PLLA matrix to prepare fully biodegradable PLLA biocomposites. The highly active nucleating surfaces of the hPLLA fiber induced chain ordering and lamellar organization, leading to a preferable formation of well-organized PLLA transcrystallinity at the surface of the hPLLA fiber under quiescent conditions. The construction of such compact transcrystallinity increased the crystallinity and enhanced the interfacial adhesion, which largely promoted heat resistance, tensile strength, and barrier property of PLLA biocomposites at a low content of hPLLA fiber. With the addition of 1 wt % hPLLA fiber, the storage modulus of the PLLA biocomposite was enhanced by 82 times from 4 to 330 MPa at 80 °C and the oxygen permeability coefficient and water permeability coefficient were decreased by 52 and 51% to be 5.9 × 10-15 cm3·cm/cm2·s·Pa and 4.5 × 10-14 g·cm/cm2·s·Pa, respectively, compared with those of pure PLLA. Moreover, the transparency of PLLA was maintained with the incorporation of hPLLA fiber. Thus, this strategy paved a new way to prepare high-performance and fully biodegradable biocomposites.

2D end-to-end carbon nanotube conductive networks in polymer nanocomposites: a conceptual design to dramatically enhance the sensitivities of strain sensors.

New generation wearable devices require mechanically compliant strain sensors with a high sensitivity in a full detecting range. Herein, novel 2D end-to-end contact conductive networks of multi-walled carbon nanotubes (MWCNTs) were designed and realized in an ethylene-α-octene block copolymer (OBC) matrix. The prepared strain sensor showed a high gauge factor (GF) of 248 even at a small strain (5%) and a linear resistance response throughout the whole strain range. The sensors also exhibited very good stretchability up to 300% and high cycling durability. This novel design solved the intrinsic problem of sensors based on carbon nanotube bundles, i.e., a long sliding phase before the disconnection of CNTs in a cost-effective and scalable way. This study rationalizes the 2D end-to-end contact concept to improve the sensitivity of the existing sensors and has great potential to be used in a wide variety of polymer based sensors.

Hierarchically interconnected porous scaffolds for phase change materials with improved thermal conductivity and efficient solar-to-electric energy conversion.

An ice-templating self-assembly strategy and a vacuum impregnation method were used to fabricate polyethylene glycol (PEG)/hierarchical porous scaffold composite phase change materials (PCMs). Hierarchically interconnected porous scaffolds of boron nitride (BN), with the aid of a small amount of graphene oxide (GO), endow the composite PCMs with high thermal conductivity, excellent shape-stability and efficient solar-to-electric energy conversion. The formation of a three-dimensional (3D) thermally conductive pathway in the composites contributes to improving the thermal conductivity up to 2.36 W m-1 K-1 at a relatively low content of BN (ca. 23 wt%). This work provides a route for thermally conductive and shape-stabilized composite PCMs used as energy storage materials.

High Efficiency Conversion of Regenerated Cellulose Hydrogel Directly to Functionalized Cellulose Nanoparticles.

This article provides a novel and efficient method of "self-assembly/modification/dispersion" for the preparation of functionalized cellulose nanoparticles (CNPs) based on regenerated cellulose hydrogel (RCH). The process of the preparation of CNPs is simplified greatly, which contributes to broadening the utilization of CNPs. Under the given conditions, cellulose chains self-assemble into nanoparticles, which connect with each other to form strings and walls of nanoparticles inside RCH. Then, RCH acts as the hydrophilic precursor of the preparation of CNPs and is modified by oligo side chains to obtain functionalized RCH with imperfect cellulose II structures. After dispersing the functionalized RCH in dimethyl sulfoxide, individual CNPs are finally isolated from functionalized RCH as a result of the decline of the crystallinity of CNPs. Obtained CNPs possess uniform size and good thermal stability, and also exhibit excellent dispersibility in organic solvents. The particle size of CNPs can be adjusted easily by oligo content and particle size of the self-assembled cellulose nanoparticles in RCH. Prepared CNPs are promising candidates for polymer modification in terms of fillers, and for biomedical fields with respect to drug delivery.

The effect of chain mobility on the coarsening process of co-continuous, immiscible polymer blends under quiescent melt annealing.

Polypropylene (PP) and five kinds of monodisperse polystyrene (PS) with different terminal relaxation times were used to explore the relationship between the mobility of polymer molecular chains and the coarsening process of immiscible polymer blends with a co-continuous morphology under quiescent melt annealing at different temperatures. The terminal relaxation time of all neat PP and PS was determined by a rheological approach to characterize the mobility of molecular chains. A selective dissolution experiment showed that all PP/PS (50/50) blends maintained a co-continuous structure during the whole annealing process. Significant coarsening behaviors were observed for all PP/PS blends under a scanning electron microscope. A linear time dependence of the size of the PS phase was found in all PP/PS blends and the coarsening phenomenon was more obvious with the decrease of the terminal relaxation time of the PS phase because of the increase of the mobility of the polymer molecular chains. A direct relationship between the phase coarsening rate and the terminal relaxation time of the PS phase was found for the first time and it satisfied the equation . According to this equation, the formulae and k ∝ Mw-1 can be derived, which can provide significant information for the control of the phase coarsening process of immiscible polymer blends with a co-continuous morphology.

Strong shear-driven large scale formation of hybrid shish-kebab in carbon nanofiber reinforced polyethylene composites during the melt second flow.

The formation of a hybrid shish-kebab (HSK) structure with different degrees of lamellar orientations was first observed in the solution crystallization of polyethylene (PE) in the presence of carbon nanofibers (CNFs). In this study, PE crystal lamellae were periodically decorated on the surface of CNFs and were aligned approximately perpendicular to the long axes of the CNFs, forming aligned hybrid shish-kebab nanostructures. More importantly, the fascinating structure was directly formed in all regions of the injection molded bars of HDPE/CNF composites, via a gas-assisted injection molding (GAIM), instead of the shell-core structure. In the GAIM process, an intense shear was imposed onto the melt during the melt second flow and drove PE chains to orient along the axes of the CNFs. Then the entropy penalty for PE chains deposited on the CNF surface was drastically decreased. Although the attractive van der Waals interactions were weak, the oriented PE chains could successfully adsorb on the CNF surface due to the decrease of the entropy penalty, therewith the underlayer coating was formed along the axis based on a two-dimensional mode for early nucleation on the CNF surface. Subsequently, subglobules appeared on the ordered structure, which could be regarded as the crystal nucleus. Finally, the oriented PE chains began to epitaxially grow from the subglobules with a folded-chain shape to decrease the polymer surface energy and grew perpendicular to the CNFs long axis, abiding by the "soft epitaxy" crystallization mechanism regardless of strict lattice matching.