Chaotropic Ions Mediated Polymer Gelation for Thermal Management.

Energy and environmental issues have increasingly garnered significant attention for sustainable development. Flexible and shape-stable phase change materials display great potential in regulation of environmental temperature for energy saving and human comfort. Here, inspired by the water absorption behavior of salt-tolerant animals and plants in salinity environment and the Hofmeister theory, highly stable phase change salogels (PCSGs) are fabricated through in situ polymerization of hydrophilic monomers in molten salt hydrates, which can serve multiple functions including thermal management patches, smart windows, and ice blocking coatings. The gelation principles of the polymer in high ion concentration solution are explored through the density functional theory simulation and verified the feasibility of four types of salt hydrates. The high concentration chaotropic ions strongly interacted with polymer chains and promoted the gelation at low polymer concentrations which derive highly-stable and ultra-moisturizing PCSGs with high latent heat (> 200 J g-1). The synergistic adhesion and transparency switching abilities accompanied with phase transition enable their smart thermal management. The study resolves the melting leakage and thermal cycling stability of salt hydrates, and open an avenue to fabricate flexible PCM of low cost, high latent heat, and long-term durability for energy-saving, ice-blocking, and thermal management.

Fabricating Freestanding, Broadband Reflective Cholesteric Liquid-Crystal Networks via Topological Tailoring of the Sm-Ch Phase Transition.

Numerous biological systems in nature provide much inspiration for humanity to master diverse coloration strategies for creating stimuli-responsive materials and display devices, such as to access gorgeous structural colors from well-defined photonic structures. Cholesteric liquid crystals (CLCs) are a fascinating genre of photonic materials displaying iridescent colors responsive to circumstance changes; however, it is still a big challenge to design materials with broadband color variation as well as good flexibility and freestanding capacity. Herein, we report a feasible and flexible strategy to fabricate cholesteric liquid-crystal networks (CLCNs) with precise colors across the entire visible spectrum through molecular structure tailoring and topology engineering and demonstrate their application as smart displays and rewritable photonic paper. Influences of chiral and achiral LC monomers on the thermochromic behaviors of CLC precursors as well as on the topology of the polymerized CLCNs are systematically investigated, demonstrating that the monoacrylate achiral LC facilitated the formation of a smectic phase-chiral phase (Sm-Ch) pretransitional phase in the CLC mixture and improved the flexibility of the photopolymerized CLCNs. High-resolution multicolor patterns in one CLCN film are generated through photomask polymerization. In addition, the freestanding CLCN films show perceivable mechanochromic behaviors and repeated erasing-rewriting performances. This work opens avenues toward the realization of pixelated colorful patterns and rewritable CLCN films promising in technology fields ranging from information storage and smart camouflage to anti-counterfeiting and smart display.

Research progress on ZnSe and ZnTe anodes for rechargeable batteries.

Transition-metal chalcogenides (TMCs) with tunable direct bandgaps and interlayer spacing are attractive for energy-related applications. Semiconducting zinc chalcogenides, especially their selenides (ZnSe) and tellurides (ZnTe), with enhanced conductivity, high theoretical capacity, low operation voltage and abundance, have appeared on the horizon and receive increasing interest in terms of electrochemical energy storage and conversion. Despite the existing typical obstruction owing to the large volume change, relatively low electrical conductivity and sluggish ion diffusion kinetics into the bulk phase, several effective strategies such as compositing, doping, nanostructuring, and electrode/cell design have exhibited promising applications. We herein provide a timely and systematic overview of recent research and significant advances regarding ZnSe, ZnTe and their hybrids/composites, covering synthesis to electrode design and to applications, especially in advanced Li/Na/K-ion batteries, as well as the reaction mechanisms thereof. It is hoped that the overview will shed new light on the development of ZnSe and ZnTe for next-generation rechargeable batteries.

Selective sequential infiltration synthesis of ZnO in the liquid crystalline phase of silicon-containing rod-coil block copolymers.

The combination of block copolymer (BCP) thin film self-assembly and selective infiltration synthesis of inorganic materials into one BCP block provides access to various organic-inorganic hybrids. Here, we apply sequential infiltration synthesis, a vapor-phase hybridization technique, to selectively introduce ZnO into the organic microdomains of silicon-containing rod-coil diblock copolymers and a triblock terpolymer, polydimethylsiloxane (PDMS)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS) and PDMS-b-polystyrene-b-PMPCS (PDMS-b-PS-b-PMPCS), in which the PMPCS rod block is a liquid crystalline polymer. The in-plane cylindrical PDMS-b-PMPCS and core-shell cylindrical and hexagonally perforated lamellar PDMS-b-PS-b-PMPCS films were infiltrated with ZnO with high selectivity to the PMPCS. The etching contrast between PDMS, PS and the ZnO-infused PMPCS enables the fabrication of ZnO/SiOx binary composites by plasma etching and reveals the core-shell morphology of the triblock terpolymer.

Shape-Stable Hydrated Salts/Polyacrylamide Phase-Change Organohydrogels for Smart Temperature Management.

Flexible and environmentally friendly phase-change materials (PCMs) with appropriate phase transition temperatures display great potential in the regulation of environmental temperature. Here, we synthesized a series of room-temperature-use phase-change organohydrogels (PCOHs) comprising phase-change hydrated salts (disodium phosphate dodecahydrate, DPDH) and polyacrylamide (PAM) glycerol hydrogels through a facile photoinitiated one-step in situ polymerization procedure. Incorporating the environmentally friendly cost-effective DPDH hydrated salts PCMs into antidrying three-dimensional (3D) networks of the PAM organohydrogel can overcome the solid rigidity and melting leakage to achieve flexibility for wearable temperature management devices. The microstructures and physical interactions among the components of the PCOHs were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and X-ray diffraction (XRD), which demonstrate that the DPDH were uniformly loaded in the networks of the PAM. Phase-change storage and thermal properties of the PCOHs were characterized by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), and the PCOHs show high energy transition efficiency and shape stability during the long-term storage and thermal cycling. Dynamic rheology and compression tests demonstrate that PCOHs can withstand a certain stress and display flexibility performance even above the melting temperature of DPDH. We also described the smart temperature management capability and the potential application of the PCOHs. This investigation offers a facile method to construct a skin-friendly flexible phase-change glycerol hydrogel and provides an alternative to the traditional melt impregnation or microencapsulation method to prepare phase-change energy storage composites.

Preparation of silver nanoparticles by solid-state redox route from hydroxyethyl cellulose for antibacterial strain sensor hydrogel.

As a smart wearable sensor device, the mildew of the biocompatible hydrogel limits its application. In this paper, silver nanoparticles were prepared by solid-state reduction of hydroxyethyl cellulose and compounded into a chemically cross-linked hydrogel as an antibacterial, flexible strain sensor. Because the high surface energy of silver nanoparticles can quench free radicals, we designed three initiators to synthesize hydrogels: ammonium persulfate (APS), 2,2'-Azobis(2-methylpropionitrile) (AIBN) and 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AIBA). Impressively, silver nanoparticles composite hydrogel could only be successfully fabricated and triggered by the AIBN. The mechanical property of the composite hydrogel (0.12 MPa at 704.33 % strain) was significantly improved because of dynamic crosslinking point by HEC. Finally, the composite hydrogels are applied to the field of antibacterial strain sensor and the highest Gauge Factor (GF) reached 4.07. This article proposes a novel, green and simple strategy for preparing silver nanoparticles and compounding them into a hydrogel system for antibacterial strain sensor.

Bending Behavior and Directed Self-Assembly of Rod-Coil Block Copolymers.

The formation of zigzags, chevrons, Y-junctions, and line segments is demonstrated in thin films formed from cylindrical morphology silicon-containing conformationally asymmetric rod-coil diblock copolymers and triblock terpolymers under solvent annealing. Directed self-assembly of the block copolymers within trenches yields well-ordered cylindrical microdomains oriented either parallel or transverse to the sidewalls depending on the chemical functionalization of the sidewalls, and the location and structure of concentric bends in the cylinders is determined by the shape of the trenches. The innate etching contrast, the spontaneous sharp bends and junctions, and the range of demonstrated periodicity and line/space ratios make these conformationally asymmetric rod-coil polymers attractive for nanoscale pattern generation.

Transparent Stretchable Dual-Network Ionogel with Temperature Tolerance for High-Performance Flexible Strain Sensors.

A stretchable transparent double network ionogel composed of physically cross-linked poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-co-HFP)) and chemically cross-linked poly(methyl methacrylate-co-butylmethacrylate) (P(MMA-co-BMA)) elastomer networks within [EMIM][TFSI] ionic liquid was fabricated through a facile one-pot thermal polymerization. The dual-network (DN) ionogel presents good mechanical performance (failure tensile stress 2.31 MPa, strain 307%) with a high loading of ionic liquid (70 wt %) for achieving required ionic conductivity (>0.1 S/m at room temperature). The transparent chemical cross-linked P(MMA-co-BMA) elastomer network endows high transparency (>93%) and high stretchability to the DN ionogel. The DN ionogel maintains good toughness, elasticity, and transparency in a wide temperature range (-40 to 80 °C) for the application in a harsh environment. In addition, the sensitivity of the DN ionogel to the change of environment temperature and deformation was detected and described. The practical potential of the DN ionogel in flexible electronic devices is further revealed by fabricating DN ionogel strain sensors to detect the movement of different human limbs including the bending of the finger, wrist, and elbow as well as the slight throat jitter during the swallowing and vocalization, showing fast response, high sensitivity, and good repeatability.

Polydopamine/polystyrene nanocomposite double-layer strain sensor hydrogel with mechanical, self-healing, adhesive and conductive properties.

Inspired by the adhesion mechanism of natural mussels, polydopamine (PDA) has been widely studied and applied in hydrogels due to its good adhesion to various materials. In this work, a double-layer hydrogel constituted of an adhesive layer and a tough layer was successfully prepared via in-situ polymerization. Adding polystyrene particles into the tough layer could improve the mechanical properties, and the adhesion of various substrates could be achieved with PDA nanoparticles in the adhesive layer. Furthermore, lithium chloride was introduced into the tough layer to endow the bilayer hydrogels with electrical conductivity. Due to the hydrophobic association in the tough layer and hydrogen bond in the adhesive layer, the double-layer hydrogel exhibits self-healing properties. In addition, the NIR light response property of PDA was beneficial to self-healing properties. As a result, it has proved that the prepared bilayer hydrogel has excellent conductivity, toughness (0.18 MPa), adhesion and self-healing properties, which is an ideal flexible wearable strain sensor with high sensitivity and good repeatability, suitable for human motion signal detection.

Vertical Lamellae Formed by Two-Step Annealing of a Rod-Coil Liquid Crystalline Block Copolymer Thin Film.

Silicon-containing block copolymer thin films with high interaction parameter and etch contrast are ideal candidates to generate robust nanotemplates for advanced nanofabrication, but they typically form in-plane oriented microdomains as a result of the dissimilar surface energies of the blocks. Here, we describe a two-step annealing method to produce vertically aligned lamellar structures in thin film of a silicon-containing rod-coil thermotropic liquid crystalline block copolymer. The rod-coil block copolymer with the volume fraction of the Si-containing block of 0.22 presents an asymmetrical lamellar structure in which the rod block forms a hexatic columnar nematic liquid crystalline phase. A solvent vapor annealing step first produces well-ordered in-plane cylinders of the Si-containing block, then a subsequent thermal annealing promotes the phase transition from in-plane cylinders to vertical lamellae. The pathways of the order-order transition were examined by microscopy and in situ using grazing incidence small-angle X-ray scattering and wide-angle X-ray scattering.

Healing, flexible, high thermal sensitive dual-network ionic conductive hydrogels for 3D linear temperature sensor.

A temperature sensor based on muti-wall carbon nanotubes (MWCNTs) composite polyacrylamide/Fe3+-polyacrylic acid (PAM/Fe3+-PAA) double network (DN) hydrogels that combines flexibility, thermal sensitivity and self-healing ability is fabricated through in situ polymerization and maceration. Due to the excellent thermal conductivity of carbon nanotubes, the temperature sensitivity of the DN hydrogels are improved and therefore can be exploited as a novel channel material for a temperature sensor. This temperature sensor can be stretched from 0 to 750% strain with the sensitivity as high as 9.4%/°Cat extreme 200% strain. Importantly, the DN hydrogels have excellent self-healing properties that it can still be stretched after cutting and healing. Similarly, the electrical and thermal sensing properties of the DN hydrogels can be self-healed analogous to the self-healing capability of human skin. In addition, DN hydrogels have high stability for bending and torsion, which can avoid errors caused by deformation in the temperature measurement. In order to attaching on nonplanar curvilinear surfaces for practical temperature detection, we designed a linear-shaped hydrogels temperature sensor, which can improve the accuracy by wrapping the surface of the measured object completely in a way that eliminates the influence of air in the holes, enabling it to be potentially integrated in soft robots to grasp real-world information for guiding their actions.

High-Strength, Self-Healable, Temperature-Sensitive, MXene-Containing Composite Hydrogel as a Smart Compression Sensor.

As a new two-dimensional material similar to graphene, MXene has attracted extensive attention in the field of electrochemical materials such as supercapacitors because of its excellent mechanical properties, electrical conductivity, and thermal conductivity. What is better than graphene is that the few-layer MXene material obtained by proper treatment has good water dispersibility and can be used as an ideal nanomaterial to enhance the conductivity of hydrogels. However, the articles about the few-layer MXene material used in the preparation of composite hydrogels are rare. In this paper, MXene was synthesized by Yury mild method. Poly(N-isopropyl acrylamide) (PNIPAM) hydrogel and physical cross-linking hydrogel were used as the matrix to prepare composite hydrogels with temperature sensitivity and stress-sensing properties. The composite hydrogels exhibited excellent mechanical properties: it could be stretched to over 14 times the original length and achieved a 0.4 MPa tensile strength while showing good self-healing ability, which was of great significance for the practical application of hydrogels. The conductivity of the composite hydrogel was 1.092 S/m, which was about 15 times that of the control hydrogel without MXene. The potential of the composite hydrogel as a smart compression sensor was also verified by the conductivity tests.

Tough hydrophobic association hydrogels with self-healing and reforming capabilities achieved by polymeric core-shell nanoparticles.

The application range of hydrogels can be greatly widened by improving their mechanical properties. It is still a great challenge to develop hydrogels with good mechanical properties, reliable self-healing properties and remolding ability at the same time. Inspired by biological soft tissue with excellent mechanical properties and self-healing properties, here, a facile method to fabricate poly (styrene-acrylic acid) (P(S-AA)) core-shell nanoparticles with plenty of carboxyl groups on their surface, and their enhancement to hydrophobic association hydrogels was reported. Under stress, the dynamic physical bonds including hydrogen bonding between polymer chains and P(S-AA) core-shell nanoparticles (NPs), and entanglement of hydrophobic chains were destroyed to effectively dissipate energy, and uniform hydrogel network leads to smooth stress-transfer, which makes the core-shell nanoparticles composite hydrophobic association hydrogels (MHA gels) excellent mechanical properties, such as excellent mechanical properties, toughness and ductility, and good self-healing properties as well. These features make the MHA gels have great potential in biomedical applications such as tissue engineering, articular cartilage and artificial skin.

Self-assembling GO/modified HEC hybrid stabilized pickering emulsions and template polymerization for biomedical hydrogels.

Graphene oxide(GO), as an amphiphilic and biocompatible material, is often used to prepare Pickering emulsion. However, the preparation of stable Pickering emulsion by a low concentration of GO is very challenging. In this research, we prepared the hydrophobic modified hydroxyethyl cellulose (mHEC) which contained quaternary ammonium group and GO which the water contact angle was 84°-86°. A stable, low cost, and biocompatible Pickering emulsion was fabricated by a low concentration of GO and different contents of mHEC. The effects of mHEC concentration, electrolyte concentration, pH, and oil/water ratio on the stability of Pickering emulsion were investigated. What's more, we prepared the biomedical macroporous polyacrylamide hydrogel by the GO/mHEC composite stabilized emulsion template for drug controlled-release. The composite hydrogel by Pickering emulsion template is a potential drug controlled-release delivery platforms. Furthermore, our strategy is extremely versatile, as Pickering particles, polymer and the monomer of hydrogel can all be varied.

Core-Shell and Zigzag Nanostructures from a Thin Film Silicon-Containing Conformationally Asymmetric Triblock Terpolymer.

The self-assembly of multiblock copolymers generates diverse hierarchical nanostructures and greatly extends the range of microdomain geometries beyond those produced by diblock copolymers. We report the synthesis of a conformationally asymmetric ABC triblock terpolymer in which the end blocks are a mesogen-jacketed liquid crystalline polymer and poly(dimethylsiloxane), respectively, and its self-assembly under mixed solvent vapor annealing forms a range of sphere, cylinder, and perforated lamellar core-shell morphologies, as well as stacked multilevel structures. Sub-7 nm diameter SiOx nanopatterns were generated by selective plasma etching of the small volume fraction Si-containing core block giving a line/space ratio of ∼1:4. Moreover, the conformational asymmetry of this terpolymer leads to zigzag cylinders on a flat substrate and stable cylinder alignment transverse to template sidewalls within lithographically patterned trenches.

Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition.

The self-assembly of a high-χ silicon-containing side-chain liquid crystalline block copolymer (LC BCP) in bulk and in thin films is reported, and the structural transition process from the hexagonally packed cylinder (HEX) to the body-centered cubic structure (BCC) in thin films was examined by both reciprocal and real space experimental methods. The block copolymer, poly(dimethylsiloxane-b-11-(4'-cyanobiphenyl-4-yloxy)undecylmethacrylate) (PDMS-b-P(4CNB11C)MA) with a molecular weight of 19.5 kg mol-1 and a volume fraction of PDMS 27% self-assembled in bulk into a hierarchical nanostructure of sub-20 nm HEX cylinders of PDMS with the P(4CNB11C)MA block exhibiting a smectic LC phase with a 1.61 nm period. The structure remained HEX as the P(4CNB11C)MA block transformed to an isotropic phase at ∼120 °C. In the thin films, the PDMS cylindrical microdomains were oriented in layers parallel to the substrate surface. The LC block formed a smectic LC phase which transformed to an isotropic phase at ∼120 °C, and the microphase-separated nanostructure transformed from HEX to BCC spheres at ∼160 °C. The hierarchical structure as well as the dynamic structural transition of the thin films were characterized using in situ grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering. The transient morphologies from the HEX to BCC structure in thin films were captured by scanning electron microscopy and atomic force microscopy, and the transition pathway was described.

Stable, Strain-Sensitive Conductive Hydrogel with Antifreezing Capability, Remoldability, and Reusability.

Conductive hydrogels have important potential in biosensors, bioactuators, and health recording electrodes, but they are often troubled by sensitivity, operating temperature range, and whether they can be recycled or not. In this paper, conductive hydrogels poly(vinyl alcohol)/glycerol/polyaniline (PGA) were prepared by organic combination of low-cost poly(vinyl alcohol) (PVA), polyaniline (PANi), and glycerin. First, the effects of PVA, glycerol, and aniline/phytic acid solution concentration on the mechanical properties, electrical properties, and frost resistance of the PGA gel were discussed. Second, the interaction energies of PVA, PANi, phytic acid, glycerol, and water molecules were analyzed by Materials Studio. Then, a simple biosensor fabricated using the PGA gel realized the detection of the conventional motion signal of the human body. The conductive gel has high sensitivity (GF = 2.14), fast response time (230 ms), and can be circulated several times (∼540 cycles). Furthermore, the PGA conductive gel can maintain good electrical conductivity (0.32 S/m) and mechanical properties even at -20 °C. Also, the gel can be recovered by injection heating, cooling, and cyclic freeze-thaw three-step method. It is believed that the PGA conductive gel would be used as a novel multifunctional material at subzero temperatures in various fields, such as flexible electrode, sensors, and wearable devices.

Extraordinary boundary morphologies of large-scale ordered domains of spheres in thin films of a narrowly dispersed diblock copolymer via thermodynamic control.

Long-range ordering of body centered cubic (BCC) spheres and various extraordinary morphologies at the boundaries of the adjacent orderly oriented domains are observed in thermally annealed thin films of a series of specific narrowly dispersed diblock copolymers, poly(dimethylsiloxane)-b-poly{2,5-bis[(4-butoxyphenyl)oxycarbonylstyrene} (PDMS-b-PBPCS, DB). The series of asymmetrical DB block copolymers (BCPs) with volume fractions of PDMS (f(PDMS)'s) from 10% to 23% self-assemble into thermodynamically stable body centered cubic (BCC) nanostructures in bulk at ambient temperature after thermal annealing. The thin films of these BCPs with a relatively large film thickness on a carbon-film coated substrate are annealed in a vacuum at 180 °C for 3 days and are characterized by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). For all thin films of these BCPs, micrometer-scale domains with a rectangular unit cell similar to the projection of the BCC lattice along the [110] direction to the substrate are observed. And the XPS results indicate that the surface layers of the thin films are composed of both PDMS and PBPCS blocks. For the thin films of the BCPs with f(PDMS) values of 10% and 13%, the neighboring [110]-oriented BCC domains match well with each other, and the boundaries are defect-free. For the thin film of the BCP with a f(PDMS) value of 23%, the PDMS spheres in the [110]-oriented BCC domains in the TEM micrograph are overlapped with each other, and interesting morphologies including defect-free interfaces, interfaces with line defects, and domains with defects and local ordering are observed at the boundaries of the neighboring [110]-oriented domains.