A Tailorable Series of Elastomeric-To-Rigid, Selfhealable, Shape Memory Bismaleimide.

In recent years, there has been rapid development in the field of shape memory materials with active deformation performance. However, bismaleimide, a widely used thermosetting material in aerospace, has been largely overlooked in shape memory applications. This work presents the synthesis of a molecule containing an alkene bond adjacent to an oxygen atom. Through molecular design, a one-time reaction between this specialized molecule and the bismaleimide molecule is successfully achieved, facilitated by the steric hindrance effect. Therefore, a new series of shape memory bismaleimide materials are obtained. By introducing a diamine to adjust the chain length, the properties of material are further improved, resulting in increasing static modulus by 506 times. The synthesized materials exhibit a broad glass transition temperature (Tg) range exceeding 153 °C, remarkable stiffness tunability. Notably, in the synthesis process of this materials series, the disulfide bonds are introduced, which facilitates the realization of self-healing and reprocessable functionalities in the resulting thermosetting materials. This significant advancement lays a solid foundation for the future recycling and reuse of aircraft, satellites, and other equipment, offering promising prospects for enhancing sustainability and efficiency within the aerospace industry.

Multifunctional UV-NIR Dual Light-Responsive Soft Actuators from a Main-Chain Azobenzene Semi-Crystalline Poly(ester-amide) Doped with Polydopamine Nanoparticles.

The development of soft photoactuators with multifunctionality and improved performance is highly important for their broad applications. Herein, we report on a facile and efficient strategy for fabricating such photoactuators with UV-NIR dual light-responsivity, room-temperature 3D shape reprogrammability and reprocessability, and photothermal healability by doping polydopamine (PDA) nanoparticles into a main-chain azobenzene semi-crystalline poly(ester-amide) (PEA). The PEA/PDA nanoparticle composite was readily processed into free-standing films with enhanced mechanical and photomechanical properties compared with the blank PEA films. Its physically crosslinked uniaxially oriented films showed rapid and highly reversible photochemically induced bending/unbending under the UV/visible light irradiation at room temperature in both the air atmosphere and water. When exposed to the NIR light, they (and their bilayer films formed with a polyimide film) exhibited photothermally induced bending even at a temperature much lower than their crystalline-to-isotropic phase transition temperature based on a unique mechanism (involving photothermally induced polymer chain relaxation due to the disruption of their hydrogen bonds). The room-temperature 3D shape reprogrammability and reprocessability and photothermal healability of the composite polymer films were also demonstrated. Such multifunctional dual light-responsive photoactuators with well-balanced mechanical robustness, actuation stability, 3D shape reprogrammability/reprocessability and photothermal healability hold much promise in various photoactuating applications.

Thiol-Aldehyde Polycondensation for Bio-based Adaptable and Degradable Phenolic Polymers.

Designing sustainable materials with tunable mechanical properties, intrinsic degradability, and recyclability from renewable biomass through a mild process has become vital in polymer science. Traditional phenolic resins are generally considered to be not degradable or recyclable. Here we report the design and synthesis of linear and network structured phenolic polymers using facile polycondensation between natural aldehyde-bearing phenolic compounds and polymercaptans. Linear phenolic products are amorphous with Tg between -9 °C and 12 °C. Cross-linked networks from vanillin and its di-aldehyde derivative exhibited excellent mechanical strength between 6-64 MPa. The connecting dithioacetals are associatively adaptable strong bonds and susceptible to degradation in oxidative conditions to regenerate vanillin. These results highlight the potential of biobased sustainable phenolic polymers with recyclability and selective degradation, as a complement to the traditional phenol-formaldehyde resins.

Sustainable Photopolymers in 3D Printing: A Review on Biobased, Biodegradable, and Recyclable Alternatives.

The global market for 3D printing materials has grown exponentially in the last decade. Today, photopolymers claim almost half of the material sales worldwide. The lack of sustainable resins, applicable in vat photopolymerization that can compete with commercial materials, however, limits the widespread adoption of this technology. The development of "green" alternatives is of great importance in order to reduce the environmental impact of additive manufacturing. This paper reviews the recent evolutions in the field of sustainable photopolymers for 3D printing. It highlights the synthesis and application of biobased resin components, such as photocurable monomers and oligomers, as well as reinforcing agents derived from natural resources. In addition, the design of biologically degradable and recyclable thermoset products in vat photopolymerization is discussed. Together, those strategies will promote the accurate and waste-free production of a new generation of 3D materials for a sustainable plastics economy in the near future.

Reprocessable Photodeformable Azobenzene Polymers.

Photodeformable azobenzene (azo) polymers are a class of smart polymers that can efficiently convert light energy into mechanical power, holding great promise in various photoactuating applications. They are typically of crosslinked polymer networks with highly oriented azo mesogens embedded inside. Upon exposure to the light of appropriate wavelength, they experience dramatic order parameter change following the configuration change of the azo units. This could result in the generation and accumulation of the gradient microscopic photomechanical force in the crosslinked polymer networks, thus leading to their macroscopic deformation. So far, a great number of photodeformable azo polymers have been developed, including some unoriented ones showing photodeformation based on different mechanisms. Among them, photodeformable azo polymers with dynamic crosslinking networks (and some uncrosslinked ones) have aroused particular interest recently because of their obvious advantages over those with stable chemical crosslinking structures such as high recyclability and reprocessability. In this paper, I provide a detailed overview of the recent progress in such reprocessable photodeformable polymers. In addition, some challenges and perspectives are also presented.

A fluorine-based strong and healable elastomer with unprecedented puncture resistance for high performance flexible electronics.

There is usually a trade-off between high mechanical strength and dynamic self-healing because the mechanisms of these properties are mutually exclusive. Herein, we design and fabricate a fluorinated phenolic polyurethane (FPPU) elastomer based on octafluoro-4,4'-biphenol to overcome this challenge. This fluorine-based motif not only tunes interchain interactions through π-π stacking between aromatic rings and free-volume among polymer chains but also improves the reversibility of phenol-carbamate bonds via electron-withdrawing effect of fluorine atoms. The developed FPPU elastomer shows the highest recorded puncture energy (648.0 mJ), high tensile strength (27.0 MPa), as well as excellent self-healing efficiency (92.3%), along with low surface energy (50.9 MJ m-2), notch-insensitivity, and reprocessability compared with non-fluorinated counterpart biphenolic polyurethane (BPPU) elastomer. Taking advantage of the above-mentioned merits of FPPU elastomer, we prepare an anti-fouling triboelectric nanogenerator (TENG) with a self-healable, and reprocessable elastic substrate. Benefiting from stronger electron affinity of fluorine atoms than hydrogen atoms, this electronic device exhibits ultrahigh peak open-circuit voltage of 302.3 V compared to the TENG fabricated from BPPU elastomer. Furthermore, a healable and stretchable conductive composite is prepared. This research provides a distinct and general pathway toward constructing high-performance elastomers and will enable a series of new applications.

High Performance and Reprocessable In Situ Generated Nanofiber Reinforced Composites Based on Liquid Crystal Polyarylate.

Polymers are playing important roles in the rapid development of triboelectric nanogenerators (TENGs); However, most polymers cannot meet the high requirements of thermomechanical performance; Thus, various polymeric composites are developed for triboelectric layer. These composites are hardly recycled since their reinforcements are unevenly distributed after reprocessing, which limits the sustainable development of TENGs. To solve the above challenges, in situ generated nanofiber reinforced composites (NFRCs) based on single-component liquid crystal polyarylate (LCP) are designed and prepared via a one-step polycondensation. Nonlinear naphthalene (NDA) widens the processing window of LCP without destabilizing the liquid crystal phase. The NDA-rich domains act as a matrix while the NDA-poor domains with higher rigidity form oriented nanofibers to achieve self-reinforcement. The resultant NFRCs possess high glass transition temperature (Tg > 220 °C) and storage modulus (E' = 0.1 GPa at 350 °C), which are far beyond existing triboelectric polymers, typically Tg < 110 °C and E' < 0.1 MPa (flowable) at 350 °C. Furthermore, NFRC-based TENG exhibits superior electrical output performance and retention rate (>90%) after reprocessing; Overall, this work offers a new design principle to prepare self-reinforced composites, which paves a way to explore high performance materials.

Reprocessable, Highly Transparent Ionic Conductive Elastomers Based on ß-Amino Ester Chemistry for Sensing Devices.

Ionic conductive elastomers (ICEs) exhibit a compelling combination of ionic conductivity and elastic properties, rendering them excellent candidates for stretchable electronics, particularly in applications like sensing devices. Despite their appeal, a significant challenge lies in the reprocessing of ICEs without compromising their performance. To address this issue, we propose a strategy that leverages covalent adaptable networks (CANs) for the preparation of ICEs. Specifically, ß-amino ester bonds as dynamic motifs are incorporated into a poly(ethylene oxide) network containing lithium bis(trifluoromethane) sulfonimide (LiTFSI) salt. LiTFSI-containing ß-amino ester networks (LBAEs) exhibit superb transparency (94%), thermal stability (>280 °C), and modest conductivity (0.00576 mS·cm-1 at 20 °C), and some LBAEs maintain operational capability across a wide temperature range (-20 to 100 °C). By regulating the lithium salt content, the mechanical properties, conductivities, and viscoelastic behaviors can be tailored. Benefiting from these features, LBAEs have been successfully applied in sensing devices for monitoring human motion (e.g., finger bending, swallowing, and clenching). Notably, even after four reprocessing cycles, LBAEs demonstrate structural integrity and maintain their operational capability. This novel approach represents a promising solution to the reprocessing challenges associated with flexible conductive devices, demonstrating the successful integration of CANs and ICEs.

Quantum Dot-Vitrimer Composites: An Approach for Reprocessable, Self-Healable, and Sustainable Luminescent Materials.

Quantum dots (QDs) are of great concern in many fields. However, they suffer from high toxicity and may lead to environmental pollution. We report the development of a QD-vitrimer composite with reprocessable, self-healable, and sustainable properties. Our QD-vitrimer composite reveals fine transparency and highly uniform QDs distribution without significant aggregation. The photoluminescence quantum yield (PLQY) is basically about four times higher than the commercial QD films. The QD-vitrimer composites can be recycled at least three times without any significant loss in structure and luminescence efficiency. A prototype light-emitting diode device is fabricated to demonstrate the promising potential of QD-vitrimer composites in real application. This research sheds light on developing environmentally friendly luminescent materials and opens up an avenue for designing advanced nanomaterials-vitrimer composites.

Self-Reporting Joule Heating Modulated Stiffness of Polymeric Nanocomposites for Shape Reconfiguration.

Shape reconfigurable devices, e.g., foldable phones, have emerged with the development of flexible electronics. But their rigid frames limit the feasible shapes for the devices. To achieve freely changeable shapes yet keep the rigidity of devices for user-friendly operations, stiffness-tunable materials are desired, especially under electrical control. However, current such systems are multilayer with at least a heater layer and a structural layer, leading to complex fabrication, high cost, and loss of reprocessability. Herein, we fabricate covalent adaptable networks-carbon nanotubes (CAN-CNT) composites to realize Joule heating controlled stiffness. The nanocomposites function as stiffness-tunable matrices, electric heaters, and softening sensors all by themselves. The self-reporting of softening is used to regulate the power control, and the sensing mechanism is investigated by simulating the CNT-polymer chain interactions at the nanoscale during the softening process. The nanocomposites not only have adjustable mechanical and thermodynamic properties but also are easy to fabricate at low cost and exhibit reprocessability and recyclability benefiting from the dynamic exchange reactions of CANs. Shape and stiffness control of flexible display systems are demonstrated with the nanocomposites as framing material, where freely reconfigurable shapes are realized to achieve convenient operation, wearing, or storage, fully exploiting their flexible potential.

Facile Preparation of Dual Functional Wearable Devices Based on Hindered Urea Bond-Integrated Reprocessable Polyurea and AgNWs.

With the advancement of material science and electronic technology, wearable devices have been integrated into daily lives, no longer just a stirring idea in science fiction. In the future, robust multifunctionalized wearable devices with low cost and long-term service life are urgently required. However, preparing multifunctional wearable devices robust enough to resist harsh conditions using a commercially available raw material through a simple process still remains challenging. In this work, reprocessable polyurea (HUBTPU) with a hard segment of hindered urea bonds (HUBs) and a soft segment of polyether is synthesized via a facile one-pot method. The robust dual functional wearable devices were obtained by simply spray-coating silver nanowires (AgNWs) on HUBTPU elastomer substrates. Due to the dynamic combination and decomposition of the HUBs and hydrogen bonds at 130 °C, the robust elastomer demonstrates favorable adhesion to various substrates. Especially, the partially embedded AgNW structure is also achieved by using ethanol as a spray solvent. The adhesion of HUBTPU substrates and embedded structure leads to stronger interfacial adhesion and stability compared to non-adhesive substrates. The as-obtained HUBTPU electrodes are able to be heated to 115 °C by applying a low voltage and sensing the strain deformation caused by human movement, which means that the electrodes are endowed with both electrical heating capability and strain sensing functionality. Therefore, this strategy reveals a potential way to prepare multifunctional wearable devices using other conductive particles and adhesive functional polymer substrates.

Fully Room-Temperature Reprogrammable, Reprocessable, and Photomobile Soft Actuators from a High-Molecular-Weight Main-Chain Azobenzene Crystalline Poly(ester-amide).

Azobenzene (azo) polymer photoactuators with full room-temperature reprogrammability, reprocessability, and photomobility are highly desirable for large-scale applications, but their development remains a daunting challenge. Herein, a strategy is first presented for fabricating such advanced photoactuators from a high-molecular-weight main-chain azo crystalline poly(ester-amide) (PEA) prepared via Michael addition polymerization. This azo PEA can be readily processed into both physically cross-linked, uniaxially oriented fibers and films with high mechanical robustness and reversible photoinduced bending/unbending at room temperature. Importantly, the presence of both amide unit-induced hydrogen bonding and crystalline domains in such films and fibers endows them with dynamic, yet stable cross-linking points, which enable their easy reprogrammability under strain at room temperature into various three-dimensional (3D) shapes (e.g., film helicoid and spiral ribbon, fiber spring) capable of showing completely different shape-dependent photomobile modes. In particular, these reshaped photoactuators can maintain their accurate 3D shapes and highly reversible photoinduced motions even after being kept at 80 °C for 20 days or at 100 °C for 2 days. They can also be reprocessed and recycled from solution at room temperature. Such a multifunctional main-chain azo crystalline PEA can serve as a versatile platform for fabricating various photoactuators with desired 3D shapes and motion modes under mild ambient conditions.

Mechanically Robust and Reprocessable Acrylate Vitrimers with Hydrogen-Bond-Integrated Networks for Photo-3D Printing.

Reprocessable acrylate vitrimer needs to enhance its strength to expand the application in photo-three-dimensional (photo-3D) printing. However, the methods for improving mechanical properties by the addition of nanofillers or a multifunctional resin into acrylate vitrimers are inappropriate for photo-3D printing due to the low curing speed of photopolymerization induced by weakening light transmittance or reduction of dimensional accuracy caused by large shrinkage. At present, we demonstrate a new strategy for developing a kind of mechanically robust and reprocessable 3D printing thermosets by combining hydrogen bonds and exchangeable ß-hydroxyl esters into acrylate vitrimers. To realize this purpose, diacrylate prepolymer containing ß-hydroxyl esters was first synthesized from glycidyl methacrylate and suberic acid. Then, the resin formulations for 3D printing comprising the synthesized diacrylate prepolymer together with acrylamide generate exchanged ß-hydroxyl ester and pendent amide in cross-linked networks. Here, hydrogen bonds resulting from the amide group as sacrificial bonds dissipate vast mechanical energy under an external load. With the inclusion of 20 wt % acrylamide, the average tensile strength and Young's modulus are up to 40.1 and 871 MPa, which increased by about 4.4 and 3.85 times, respectively. The network rearrangement of cross-linked vitrimers can be achieved through the dynamic ester exchange reactions with gradual disappearance of hydrogen bonds at elevated temperatures, imparting reprocessability into the printed structures. Various photo-3D printing or UV irradiation shapes were successfully produced, and these dissolved in ethylene glycol could be remolded again.

Degradable Poly(vinyl alcohol)-Based Supramolecular Plastics with High Mechanical Strength in a Watery Environment.

It is challenging to fabricate degradable poly(vinyl alcohol) (PVA)-based plastics that can be used in watery environments because PVA is soluble in water. In this study, PVA-based supramolecular plastics with excellent degradability in soil and high mechanical strength in watery environments are fabricated by the complexation of vanillin-grafted PVA (VPVA), hydrophobic humic acid (HA), and Fe3+ ions (hereafter denoted as VPVA-HA-Fe complexes). Large-area PVA-based plastics can be easily prepared from a solution of VPVA-HA-Fe complexes using a blade-coating method. The high-density of hydrogen bonds and coordination interactions, as well as the reinforcement of self-assembled Fe3+ -chelated HA nanoparticles, facilitate the fabrication of PVA-based plastics with a breaking strength of ≈85.0 MPa. After immersion in water at room temperature for 7 d, the PVA-based plastics exhibit a breaking strength of ≈26.2 MPa, which is similar to that of polyethylene in its dry state. Furthermore, owing to the reversibility of the hydrogen bonds and coordination interactions, the VPVA-HA-Fe plastics are recyclable and can be conveniently processed into plastic products with desired shapes. After being placed under soil for ≈108 d, the PVA-based plastics are completely degraded into nontoxic species without requiring manual interference.

Reconfigurable and Recyclable Photoactuators Based on Azobenzene-Containing Polymers.

Photoactuators are promising smart materials that can adapt their shapes upon light illumination. Smart materials with recycling, reusable, and reconfigurable properties are crucial for a sustainable society, and it is important to expand their function. Recently, much effort was made to address the issue of reprocessability and recyclability of photoactuators. Based on the development of polymer chemistry, supramolecular chemistry, and dynamic covalent chemistry, it is now possible to prepare reconfigurable and recyclable photoactuators using azobenzene-containing polymers (azopolymers). Herein, the recent advances on reconfigurable and reprocessable photoactuators, including dynamic crosslinked networks systems and non-covalently crosslinked azobenzene-containing polymers, were reviewed. We discuss the challenges in the field as well as the directions for the development of such photoactuators.

Tunable Photocontrolled Motions Using Stored Strain Energy in Malleable Azobenzene Liquid Crystalline Polymer Actuators.

A new strategy for enhancing the photoinduced mechanical force is demonstrated using a reprocessable azobenzene-containing liquid crystalline network (LCN). The basic idea is to store mechanical strain energy in the polymer beforehand so that UV light can then be used to generate a mechanical force not only from the direct light to mechanical energy conversion upon the trans-cis photoisomerization of azobenzene mesogens but also from the light-triggered release of the prestored strain energy. It is shown that the two mechanisms can add up to result in unprecedented photoindued mechanical force. Together with the malleability of the polymer stemming from the use of dynamic covalent bonds for chain crosslinking, large-size polymer photoactuators in the form of wheels or spring-like "motors" can be constructed, and, by adjusting the amount of prestored strain energy in the polymer, a variety of robust, light-driven motions with tunable rolling or moving direction and speed can be achieved. The approach of prestoring a controllable amount of strain energy to obtain a strong and tunable photoinduced mechanical force in azobenzene LCN can be further explored for applications of light-driven polymer actuators.