The design and synthesis of supramolecular self‐healing polymers with high healing efficiency and excellent integrated mechanical properties is challenging due to conflicting attributes of dynamic self‐healing and mechanical properties. Herein, this study introduces a design concept, that is, “dynamic hard domains,” to balance self‐healing performance, mechanical strength, elastic recovery, and at the same time obtain extreme toughness. The essential features of the dynamic hard domains include: (i) a noncrystallized and loose structure, (ii) low binding energy and high mobility, and (iii) sequential dissociation and rapid rearrangement. Based on this strategy, a simple one‐step polycondensation route is reported to synthesize a transparent polyurethane‐urea supramolecular elastomer (PPGTD‐IDA), which successfully combines decent mechanical strength, extreme toughness, outstanding notch‐sensitiveness, self‐recoverability, and room‐temperature self‐healing. Upon rupture, the PPGTD‐IDA completely restores the mechanical properties within 48 h. Furthermore, the results demonstrate repeatable healing of mechanical properties and prominent antiaging healability. Taking advantages of merits of PPGTD‐IDA, it can be utilized for fabricating impact‐resistant materials for protection of aluminum alloys as well as stretchable and self‐healing conductors, which exhibits unique characteristics such as stable conductivity during stretching (even after healing or with notch), and automatic elimination of the notch during stretching/releasing cycles.
For the first time, mesoporous Fe3O4@ZnO sphere decorated graphene (GN-pFe3O4@ZnO) composites with uniform size, considerable porosity, high magnetization and extraordinary electromagnetic (EM) wave absorption properties were synthesized by a simple and efficient three-step method. Structure and morphology details were characterized by X-ray diffraction, transmission electron microscopy, high-resolution electron microscopy and field-emission scanning electron microscopy. Electron microscopy images reveal that pFe3O4@ZnO spheres with obvious porous and core-shell structures are uniformly coated on both sides of the GN sheets without significant numbers of vacancies or apparent aggregation. EM wave absorption properties of epoxy containing 30 wt% GN-pFe3O4@ZnO were investigated at room temperature in the frequency region of 0.2-18 GHz. The absorption bandwidth with reflection loss (RL) values less than -10 dB is up to 11.4 GHz, and the minimal RL is almost -40 dB. The intrinsic physical and chemical properties of the materials, the synergy of Fe3O4 and ZnO, and particularly the unique multi-interfaces are fundamental to the enhancement of EM absorption properties. The as-prepared GN-pFe3O4@ZnO composites are shown to be lightweight, have strong absorption, and broad frequency bandwidth EM absorbers.
Stretchable and autonomously self-healable elastomers with wide-ranging tunable mechanical properties have attracted increasing attention in various industries. To date, it continues to be a huge challenge to synthesize selfhealing elastomers integrating extreme stretchability, relatively high mechanical modulus, and autonomous and rapid selfhealing capability. Herein, we propose a novel covalent/ supramolecular hybrid construction strategy, in which the covalent cross-links are responsible for providing high modulus and elasticity, while supramolecular cross-links realize extreme stretchability and rapid self-healing under room temperature depending on the ultrafast exchange kinetics of metal−ligand motifs and multicoordination modes. The representative polyurea hybrid elastomer, CSH-PPG-Zn-0.25, can be stretched more than 180× its original length with the highest Young's modulus (1.78 ± 0.08 MPa) among reported ultrastretchable materials. CSH-PPG-Zn-0.25 can fully restore mechanical properties of completely cut samples within 3 h. Note that the healing process can take place under a low temperature of −20 °C and unaffected by surface aging and atmospheric moisture. Merely tailoring the molar ratio of metal/ligand actualizes wide-ranging tunability of mechanical and dynamic properties, such as Young's modulus (from 1.71 ± 0.08 MPa to 5.56 ± 0.22 MPa), maximum tensile strength (from 0.32 ± 0.03 MPa to 4.42 ± 0.23 MPa), strain at break (from >18000% to 630 ± 27%), and storage modulus, ascribed to the increase of cross-linking density and formation of stiff ionic clusters. On the basis of the different material characteristics, two typical elastomers are employed, respectively, as flexible and self-healable conductor and self-healable automotive paint. Benefiting from the fantastic antiaging and low-temperature healing features of CSH-PPG-Zn-0.25, the prepared Ag-NWs/ CSH-PPG-Zn-0.25 conductor can even regain its conductive function below zero. CSH-PPG-Zn-0.50 material, meeting the strict mechanical requirements of automotive paints, is able to thoroughly eliminate the surface scratches and recover anticorrosion function in the local damaged region under the atmospheric environment.
Self-healing polymers
with microphase-separated structure are plagued
with inferior self-healing efficiency at room temperature due to a
lack of dynamic interactions in hard domains. Herein, we describe
a novel strategy of multiphase active hydrogen bonds (H-bonds), toward
realizing fast and efficient self-healing at room temperature, even
under harsh conditions. The core conception is to incorporate thiourea
moieties into microphase-separated polyurea network to form multistrength
H-bonds, which destroy the crystallization of hard domains and, at
the same time, insert the dynamic reversible H-bonds in both hard
and soft segments, accounting for the surprisingly self-healing performances.
The synthesized polymeric material, poly(dimethylsiloxane)–4,4′-methylenebis(phenyl
isocyanate)–1,1′-thiocarbonyldiimidazole, completely
recovers all of the mechanical properties within 4 h at room temperature
after rupture. Significantly, self-healing process can also take place
at low temperature (restoration with an 85% efficiency in 48 h at
−20 °C) or in the water (restoration with a 95% efficiency
in 4 h). Depending on the cleavage/reformation of multiphase H-bonds,
the material exhibits unprecedented ultrastrechability and notch-insensitiveness.
It can be stretched up to 31 500% without fracture and reach
a notch-insensitive stretching of up to 18 000%. These exceptional
characteristics inspired us to fabricate highly stretchable self-healable
underwater conductor and protective self-healing film for suppressing
shuttling of polysulfides and preventing crack propagation in S cathode,
which provide the pathway for applications in underwater electronic
devices or advanced Li–S batteries.
Corrosion potential stimulus-responsive smart nanocontainers (CP-SNCs) are designed and synthesized based on the installation of the supramolecular assemblies (bipyridinium ⊂ water-soluble pillar[5]arenes) onto the exterior surface of magnetic nanovehicles (FeO@mSiO), linked by disulfide linkers. The supramolecular assemblies with high binding affinity as gatekeepers effectively block the encapsulated organic corrosion inhibitor, 8-hydroxyquinoline (8-HQ), within the mesopores of FeO@mSiO. When the corrosion potential of the magnesium alloy (-1.5 V vs SHE) is exerted, 8-HQ is released instantly because of the cleavage of disulfide linkers and the removal of the supramolecular assemblies. CP-SNCs were incorporated into the hybrid organic-inorganic sol-gel coating to construct a corrosion potential stimulus-feedback anticorrosion coating (CP-SFAC) that was then deposited on the magnesium alloy, AZ31B. With the aid of a magnetic field, CP-SNCs were gathered in the proximity of the surface of AZ31B. CP-SFAC showed a satisfactory anticorrosion performance, more importantly, through the evaluation of microzone electrochemical techniques. CP-SFAC presented the rapid self-healing functionality when the localized corrosion occurred. Shortening the distance between CP-SNCs and the surface of AZ31B enhances the availability of the incorporated CP-SNCs and makes most of the CP-SNCs to timely respond to the corrosion potential stimulus and facilitates the formation of a compact molecular protective film before the corrosion products pile up. The characteristics of fast response time and quick self-healing rate meet the requirements of the magnesium alloy for self-healing in local regions.
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