Highly Transparent and Colorless Self‐Healing Polyacrylate Coatings Based on Diels–Alder Chemistry

The efficient integration of reversible polymer networks into acrylate‐based polymeric materials is of peculiar interest for the development of coatings that combine high transparency with self‐healing ability. In this work, reversible networks are obtained by reacting a series of linear copolymers of furfuryl methacrylate with aliphatic bismaleimides through Diels–Alder (DA) reaction between furan and maleimide moieties. Owing to dynamic crosslinking, the obtained coatings exhibit thermal reversibility, as determined by differential scanning calorimetry and dissolution experiments. Furthermore, upon heating over the retro‐DA temperature, an excellent recovery of mechanically induced surface damages proves successful thermal remendability. Compared to previous reports on DA‐based acrylate networks, the presented thermally responsive coatings exhibit outstanding transparency and absence of color, as a result of an accurate choice of suitable monomeric precursors. In addition, a pronounced hydrophobic behavior and excellent adhesive properties make the proposed material particularly suitable for optical applications.     

Transparent Surfactant/Epoxy Composite Coatings with Self‐Healing and Superhydrophilic Properties

In this paper, highly transparent, robust, and superhydrophilic polyethylene glycol tert‐octylphenyl ether nonionic surfactant/epoxy (Triton X‐100/epoxy, TXE) composite coatings are successfully prepared with a facile, one‐step drop‐casting method by mixing Triton X‐100 with an epoxy resin and an amine curing agent. The hydrogen bond reaction between the hydroxyl group of Triton X‐100 and the ether group of the epoxy resin improves the compatibility and reduces the glass transition temperature (T_g) of the TXE composite coatings. The free Triton X‐100 surfactant easily accumulates on the surface of the TXE composite coatings, which improves the hydrophilicity of the TXE composite coatings. The TXE composite coatings are self‐healable because of their low T_g and the migration of Triton X‐100 small molecule surfactant. Any damage arising from denting, cutting, or wiping by tetrahydrofuran can be healed, and the composite coating can regain its superhydrophilic properties through a heating process. The TXE composite coatings demonstrate excellent acid, alkali, salt, high temperature, and ultrasonic‐resistant properties. This facile preparation technique has the potential to be applied in the scalable fabrication of multifunctional coatings in anti‐fogging, oil–water separation, and optical–electric devices.     

Comparatively Thermal and Crystalline Study of Poly(methyl‐methacrylate)/Polyacrylonitrile Hybrids: Core–Shell Hollow Fibers,Porous Fibers,and Thin Films

The polyacrylonitrile/polymethyl‐methacrylate (PMMA/PAN) porous fibers, core–shell hollow fibers, and porous thin films are prepared by coaxial electrospinning, single electrospinning, and spin‐coating technologies, respectively. The different morphologies arising from different processes display great influences on their thermal and crystalline properties. The adding of PMMA causes porous structure due to the microphase‐separation structure of immiscible PMMA and PAN phases. The lower weight loss, higher degradation temperature, and glass‐transition temperatures of porous thin films than those of porous fibers and core–shell hollow fibers are obtained, evidencing that the polymer morphologies produced from the different process can efficiently influence their physical properties. The orthorhombic structure of PAN crystals are found in the PMMA/PAN porous thin films, but the rotational disorder PAN crystals due to intermolecular packing are observed in the PMMA/PAN porous fibers and core–shell hollow fibers, indicating that different processes cause different types of PAN crystals.

     

Self‐Healing Epoxy Coatings via Focused Sunlight Based on Photothermal Effect

Epoxy coatings which can be healed via photothermal effect from focused sunlight are reported. The diamine of m‐xylylenediamine (MXDA) and monoamine of 4‐(heptadecafluorooctyl)aniline (HFOA) are reacted into the diglycidylether of bisphenol A (DGEBA) network. Via gradual replacement of MXDA with HFOA, the glass transition temperature and crosslinking density of the epoxy network are tuned to achieve the thermally induced healing based on chain diffusion and reentanglement. Aniline black (AB) with well absorptivity for sunlight is used subsequently as the organic photothermal compound, transferring the thermally induced healing into a sunlight responsive one. A common handheld magnifier, which can focus natural sunlight to the required power density (0.6–0.9 W cm⁻¹), is used to successfully heal one cracked coating in outdoor circumstance. This study provides a potential approach to achieve the convenient, precise, and timely healing for outdoor epoxy coatings.

     

Dual Cross‐Linked Hydrogels with High Strength,Toughness, and Rapid Self‐Recovery Using Dynamic Metal–Ligand Interactions

A dual cross‐linking design principle enables access to hydrogels with high strength, toughness, fast self‐recovery, and robust fatigue resistant properties. Imidazole (IMZ) containing random poly(acrylamide‐co‐vinylimidazole) based hydrogels are synthesized in the presence of Ni²⁺ ions with low density of chemical cross‐linking. The IMZ‐Ni²⁺ metal–ligand cross‐links act as sacrificial motifs to effectively dissipate energy during mechanical loading of the hydrogel. The hydrogel mechanical properties can be tuned by varying the mol% of vinylimidazole (VIMZ) in the copolymer and by changing the VIMZ/Ni²⁺ ratio. The resultant metallogels under optimal conditions (15 mol% VIMZ and VIMZ/Ni²⁺ = 2:1) show the best mechanical properties such as high tensile strength (750 kPa) and elastic modulus (190 kPa), combined with high fracture energy (1580 J m^?2) and stretchability (800–900% strain). The hydrogels are pH responsive and the extent of energy dissipation can be drastically reduced by exposure to acidic pH. These hydrogels also exhibit excellent anti‐fatigue properties (complete recovery of dissipated energy within 10 min after ten successive loading–unloading cycles at 400% strain), high compressive strength without fracture (17 MPa at 96% strain), and self‐healing capability due to the reversible dissociation and re‐association of the metal ion mediated cross‐links.     

Core–Shell Structured Cellulose Nanofibers/Graphene@Polypyrrole Microfibers for All‐Solid‐State Wearable Supercapacitors with Enhanced Electrochemical Performance

Thanks to their considerable electrochemical and mechanical properties, fiber‐shaped supercapacitors have become the most potential energy storage devices for portable and wearable electronics in the future; however, challenges still exist in the pursuit of practical applications among them. In this work, ternary microfibers, which are composed of TEMPO‐oxidized cellulose nanofibers/reduced graphene oxide microfiber cores coated with polypyrrole shell layers, are successfully fabricated through industrializable and sustainable wet‐spinning and interfacial polymerization strategies. The prepared microfibers possess well‐defined microstructures and outstanding mechanical properties (559 MPa). When assembled into symmetrical all‐solid‐state fiber‐shaped supercapacitors (FSCs), they exhibit remarkable electrochemical properties (647 mF cm^?2, 14.37 µWh cm^?2 at 0.1 mA cm^?2), prominent cycling stability (92.5% capacitance retention and 92.6% coulomb efficiency after 10 000 cycles), and extraordinary flexibility (no significant decay in capacitance after 5000 bending cycles), which are superior to all the congeneric FSCs reported to date. The prominent performances are ascribed to the synergistic effect of the well‐designed ternary system and synergistic effects between interior components. The advantages in electrochemical, mechanical, and industrial properties of the ternary FSCs can provide reference and boost the development of flexible energy storage applications.     

Super‐Tough,Self‐Healing Polyurethane Based on Diels‐Alder Bonds and Dynamic Zinc–Ligand Interactions

Self‐healing polymer materials have attracted extensive attention and have been explored due to their ability of crack repairing in materials. This paper aims to develop a novel polyurethane‐based material with high self‐healing efficiency and excellent mechanical properties under 80 °C on the basis of reversible Diels–Alder bonds as well as zinc–ligand structure (DA‐ZN‐PU). By integrating DA bonds and zinc–ligand structure, as‐prepared DA‐ZN‐PU samples reach the maximum tensile strength as much as 28.45 MPa. After self‐healing, the tensile strength is 25.85 MPa, leading to the high self‐healing efficiency of 90.8%. In addition, by introducing carbonyl iron powder (CIP), a new polyurethane containing carbonyl iron powder (DA‐ZN‐CIP‐PU) can be achieved, exhibiting microwave‐assisted self‐healing property. And the self‐healing efficiency can be reached to 92.6% in 3 min. Due to high self‐healing efficiency and excellent mechanical properties of the prepared novel polyurethane, it has application attributes in crack repair of functional composite materials.     

Ultra‐Fast Microwave Assisted Self‐Healing of Covalent Adaptive Polyurethane Networks with Carbon Nanotubes

Vitrimers are a class of covalent adaptive networks which, unlike other covalent networks, can be thermally reprocessed, recycled, and are self‐healing. In this research, a polyurethane vitrimer network is prepared using 1,4‐phenylene diisocyanate and excess amount of polycaprolactone polyol. The dynamic nature of this network is provided by a dual effect of dynamic transesterification reactions as well as dynamic transcarbamoylation reactions. This vitrimer can be reshaped, be recycled, and heal potential defects at high enough temperatures. A fast healing strategy is developed by the addition of small amounts (0.05 wt%) of carbon nanotubes (CNTs) which enables the use of microwave radiation for an efficient fast healing process. Using this strategy the healing time decreases more than 30 times compared to using a conventional oven. CNTs also enhance the vitrimer mechanical properties and compensate for the mechanical property loss of the dynamic PU network in comparison to the permanent PU network.     

Facile Preparation of Polydimethylsiloxane Elastomer with Self‐Healing Property and Remoldability Based on Diels–Alder Chemistry

The polydimethylisioxane elastomer based on Diels–Alder (DA) chemistry is successfully prepared by directly crosslinking bis(3‐aminopropyl)‐terminated polydimethylsiloxane with the bisepoxide containing two DA bonds in one molecule via epoxy‐amine reaction. The elastomer prepared based on DA chemistry exhibits good mechanical property, high self‐healing, and remolded efficiencies. The as‐prepared elastomer can be stretched to over 400% and its tensile strength can reach 0.80 MPa. The self‐healing efficiency and remolded efficiency are up to 93% and 95%, respectively. This work provides a simple and efficient way to fabricate the self‐healing and remolded polydimethylsiloxane elastomer with good mechanical properties. The as‐prepared elastomer has a promising potential in artificial muscles, protective coatings, and intelligent flexible electronics.     

Preparation of core–shell glass bead/polysulfone microspheres with two‐step sol–gel process

Core–shell microspheres made from glass beads as the core phase and polysulfone (PSf) as the shell phase can act as an absorbent in the separation process or a supporter for chemical reactions. Based on phase‐inversion principles, a two‐step sol–gel method was developed in this work in which ether was added first and H₂O was added second to a PSf‐containing dimethyformamide (DMF) solution to help PSf solidify on the surface of glass beads. The results from scanning electron microscopy, Fourier transform IR, and X‐ray photoelectron spectroscopy showed that a dense layer of PSf (thin to several microns) was coated on the glass beads and the core–shell microspheres were almost monodispersed. The utilization percentages of the glass beads and PSf were high as 100 and 80%, respectively. The thickness of the PSf membrane was calculated to be about 4.3 μm. To obtain well‐monodispersed microspheres, the practical volume ratio of ether to DMF was recommended to be larger than 4.5. The results suggested that the two‐step sol–gel method is a highly efficient process for preparation of glass bead/PSf core–shell microspheres. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3365–3369, 2006     

Design Strategy for the Multilayer Core–Shell Bioceramics with Controlled Chemistry

New strategies for fabricating multiphase bioceramic porous scaffolds with time‐dependent biodegradation and pore network enlargement are of fundamental importance in the advancement of bioceramics. Here, we developed a one‐step preparation of core–shell bioceramic microspheres (~2 mm in diameter) with single‐ or double‐shell structure through a coaxially aligned multilayer capillary system. The Ca‐phosphate (CaP) and Ca‐silicate (CaSi) ceramic phase distribution could be also adjusted by extruding through different capillaries, and thus the biodegradation rate would be readily tailored over time. When the polystyrene (PS) microbeads of ~15 μm in diameter were premixed into the CaP‐ or CaSi‐containing alginate slurry, the tailorable porous structures could be introduced into the core or different shell layers of the microspheres. These micropores may potentially maximize the permeability for rapid exchange of guest molecules or inorganic ions from the bioceramics. Totally, such strategy is promising because the ceramic phases with different biological properties can be assembled into the core–shell bioceramic microspheres, and thus the macropore structure evolution may be readily manipulated in the closely packed microsphere systems. We believe our gradient hybrid methodology will have potential in various categories of advanced biomaterials of organic–inorganic composites.     

Impact Modification and Fracture Mechanisms of Core–Shell Particle Reinforced Thermoplastic Protein

Mechanical properties and fracture mechanisms of Novatein thermoplastic protein and blends with core–shell particles (CSPs) have been examined. Novatein is brittle with low impact strength and energy‐to‐break. Epoxy‐modified CSPs increase notched and unnotched impact strength, tensile strain‐at‐break, and energy‐to‐break, while tensile strength and modulus decrease as CSP content increases. T_g increases slightly with increasing CSP content attributed to physical crosslinking. Changes to mechanical properties are related to the critical matrix ligament thickness and rate of loading. Novatein control samples display brittle fracture characterized by large‐scale crazing. At high CSP content a large plastic zone and a slow crack propagation zone in unnotched and tensile samples are observed suggesting increased energy absorption. Notched impact samples reach critical craze stresses easily regardless of CSP content reducing impact strength. It is concluded that the impact strength of thermoplastic protein can be modified in a similar manner to traditional thermoplastics.

     

Self‐Detecting and Self‐Healing Reinforce Elastomer Doped with Aggregation‐Induced Emission Molecules

Most of elastomers for fabrication of comfortable epidermal devices and smart actuators produce responsive signals by the stimuli‐induced deformation. Herein, a dynamic visualization of external stimuli rather than the deformation through synthesis of a self‐healing poly(dimethylsiloxane) (PDMS)‐based elastomer doped with aggregation‐induced emission (AIE) molecules is reported. The self‐healing PDMS‐based elastomer is designed and synthesized through molecule integration of reversible multi‐strength H‐bonds and permanent covalent crosslink sites. The adjustment of the weight ratio of elastic cross‐linker offers tunable mechanical properties of the resultant elastomer. After doping such an elastomer with AIE molecules of 1,1,2,2‐tetrakis(4‐nitrophenyl)ethane, the elastomer composite displays strong on–off fluorescence depending upon mechanical damage and temperatures, which can be used to detect the breaking and self‐healing performances, as well as the temperature change. The strategy described here provides another way to develop smart polymeric elastomers for practical applications.     

Tailor‐Made Functional Polymethacrylates with Dual Characteristics of Self‐Healing and Shape‐Memory Based on Dynamic Covalent Chemistry

New shape memory polymers with self‐healing behavior are obtained by thermoreversible Diels–Alder (DA) cross‐linking of a furfuryl group‐containing star‐block copolymer with 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide. The star‐block copolymer consisting of a 3‐arm polycaprolactone (PCL) core and a polyfurfuryl methacrylate shell is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. For this, a 3‐arm macro‐RAFT agent based on PCL is converted with an appropriate amount of furfuryl methacrylate in the presence of a radical initiator. Films of the DA network are partly insoluble at ambient temperatures. After annealing at 120 °C the films become completely soluble because of the progressing retro‐DA reaction. Evaporation of the solvent and subsequent annealing at 60 °C restores the original insoluble state of the material. By means of a scratch test and tensile tests on cut and subsequently mended samples it is shown that the retro‐DA reaction facilitates self‐healing. Additionally, the films show pronounced shape memory effects with reasonable shape recovery and fixity ratios, which are attributed to the melting and crystallization of the PCL phase.     

Preparation of novel hybrid inorganic–organic hollow microspheres via a self‐template approach

BACKGROUND: Hollow microspheres, especially biodegradable polymeric microspheres, have attracted considerable attention due to their particular characteristics. Up to now, microspheres have been prepared via various strategies, for instance the template synthesis method and the self‐assembly process. However, economic, novel and simple methods to prepare hollow microspheres are still being sought. RESULTS: Phosphazene‐containing microspheres, which contain self‐assembled core‐shell structures, were prepared at high colloid contents using an ultrasonic bath via a self‐template approach. Along with the controlled self‐degradation of the internal core, the corresponding hybrid inorganic–organic hollow microspheres appeared. The mechanism was evidenced by means of transmission and scanning electron microscopy, cross‐polarization with magic angle spinning NMR, Fourier transform infrared spectroscopy, X‐ray diffraction and thermogravimetric analysis. CONCLUSION: It was clarified that the phosphazene‐containing microspheres could be formed and stably dispersed without aggregation even at high colloid contents using the ultrasonic bath method and the microspheres contain self‐assembled core–shell structures. Along with the controlled self‐degradation of the internal core, the corresponding hollow microspheres appeared. The mechanism of this preparation is of great significance because it is completely different from the conventional template synthesis method and the self‐assembly process. The absence of any stabilizing agent and special templates might inspire creative imagination in the design of new morphologies of micro‐ and nanostructures. Copyright © 2007 Society of Chemical Industry     

Enhancement of Mechanical and Self‐Healing Performance in Multiwall Carbon Nanotube/Rubber Composites via Diels–Alder Bonding

Mechanically robust and self‐healing rubbers are highly desired to satisfy the increasing demand of high‐performance smart tires and related materials. Herein, a self‐healing rubber nanocomposite with enhanced mechanical and self‐healing performance based on Diels–Alder chemistry has been investigated. The furfuryl grafted styrene‐butadiene rubber and furfuryl terminated MWCNT (MWCNT‐FA) are reacted with bifunctional maleimide to form a covalently bonded and reversibly cross‐linked rubber composite. Obvious reinforcing effect is obtained at high cross‐linking density. Over 200–300% increase in the Young's modulus and toughness can be achieved in the rubber nanocomposites with 5 wt% MWCNT‐FA. Meanwhile, the healing efficiency increased with MWCNT‐FA content. MWCNT‐FA plays dual roles of effective reinforcer and a kind of healant.

     

Comparison of styrene reversible addition–fragmentation chain‐transfer polymerization in a miniemulsion system stabilized by ammonlysis poly(styrene‐alt‐maleic anhydride) and sodium dodecyl sulfate

In this study, we conducted the reversible addition–fragmentation chain‐transfer (RAFT) polymerization of styrene (St) in a miniemulsion system stabilized by two different stabilizers, ammonlysis poly(styrene‐alt‐maleic anhydride) (SMA) and sodium dodecyl sulfate (SDS), with identical reaction conditions. The main objective was to compare the polymerization kinetics, living character, latex stability, and particle morphology. The macro‐RAFT agent used in both systems was SMA, which was obtained by RAFT solution polymerization mediated by 1‐phenylethyl phenyldithioacetate. The experimental results show that the St RAFT miniemulsion polymerization stabilized by SDS exhibited a better living character than that stabilized by ammonlysis SMA. The final latices were very stable in two systems, but different stabilizers had an obvious effect on the polymerization kinetics, living character, and particle morphology. All of the particles obtained by RAFT miniemulsion polymerization stabilized by SDS were solid, but an obvious core–shell structure was observed in the miniemulsion system stabilized by ammonlysis SMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Tannin‐Tethered Gelatin Hydrogels with Considerable Self‐Healing and Adhesive Performances

Hydrogels, especially the ones with self‐recovery and adhesive performances, have attracted more and more attention owing to their wide practical potential in the biomedical field involving cell delivery, wound filling, and tissue engineering. Tannic acid (TA), a nature‐derived gallol‐rich polyphenol, exhibits not only unique chelating properties with transition metal cations but also desirable anti‐oxidation properties and strong bonding capability to proteins and gelatin. Thus, taking advantage of the versatility of TA, a one‐pot method is proposed herein to produce TA‐modified gelatin hydrogels with the aid of NaIO₄ under basic conditions. By changing the amount of NaIO₄ used, the obtained hydrogels are covalently cross‐linked to different degrees and consequently exhibit diversity in their self‐healing and adhesive properties. The gelling time, viscoelasticity, and morphology of hydrogels are investigated, and when the feed molar ratio of NaIO₄ to TA is adjusted to 15:1, the fabricated hydrogel shows optimum self‐healing efficiency of 73% and adhesive strength of 36 kPa. Additionally, considering the completely natural origin of TA and gelatin, this study offers an original way for the fabrication of biocompatible self‐healing and adhesive materials.     

Core–shell latex particles consisting of polysiloxane–poly(styrene-methyl methacrylate-acrylic acid): Preparation and pore generation

Latexes with a poly(dimethyl siloxane) core and a poly(styrene-methyl methacrylate-acrylic acid) [poly(St-MMA-AA)] shell have been prepared in two steps in order to generate particles that have a core with a very low glass transition temperature. In the first step, poly(dimethyl siloxane) particles were obtained via the ring-opening emulsion polymerization of octamethyl tetracyclosiloxane (D₄). The polymerization was carried out using either an anionic or a cationic catalyst. In the first case, sodium hydroxide was used as catalyst and sodium dodecylbenzene sulfonate as surfactant, while in the second, the alkylbenzene sulfonic acid (ABSA) was used both as catalyst and surfactant. Using a PD₄ latex as seed, a seeded emulsion polymerization of St-MMA-AA was conducted to obtain PD₄–P(St-MMA-AA) core–shell particles. Numerous recipes were attempted and the most successful were those in which the seed was prepared with a cationic catalyst (ABSA) at a relatively low temperature (75°C). The core–shell structure of the particles was identified by transmission electron microscopy, but also via wetting angle, water absorption, and T_g measurements. Finally, pores were generated in the core–shell particles via an alkali–acid treatment. Because PD₄ has a very low glass transition temperature, it cannot be easily handled. However, protected by a shell, it could be used as a constituent of composite materials with enhanced impact strength, even at very low temperatures. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2235–2245, 1999