Dynamic and Reprocessable Fluorinated Poly(hindered urea) Network Materials Containing Ionic Liquids to Enhance Triboelectric Performance.

Triboelectric nanogenerators (TENGs), a newly developed energy harvesting device that converts surrounding environmental mechanical stimuli into electricity, have been significantly explored as an ideal long-term power source for electrical devices. Despite recent advances, the development of advanced TENG devices with sufficient outputs to sustainably power electronic devices and rapid self-healability under mild conditions to improve their lifetime and function is highly demanded. Here, we report a robust self-healable and reprocessable TENG fabricated with a covalent adaptive network based on mechanically strong fluorinated poly(hindered urea) (F-PHU) integrated with ionic liquid as an efficient dielectric material to improve its triboelectric efficiency and self-healing capability simultaneously. The synthesis and integration of a well-defined reactive copolymer having both pendant fluorinated and t-butylamino bulky groups are the key to fabricate robust F-PHU networks containing fluorinated dangling chains that can interact with ionic liquids to induce ionic polarization, which raises the dielectric constant and thus increases triboelectric performance. They also are cross-linked with dynamic bulky urea linkages for rapid self-healability and high reprocessability through their reversible exchange reactions at moderate temperatures. The developed ionic F-PHU materials exhibit a high TENG output performance (power density of 173.0 mW/m2) as well as high TENG output recovery upon repairing their surface damages. This work demonstrates that such a synergistic design of triboelectric ionic F-PHU materials could have great potential for applications requiring high-performance and long-lasting energy harvesting.

Dynamic Covalent Polyurethane Network Materials: Synthesis and Self-Healability.

Polyurethane (PU) has not only been widely used in the daily lives, but also extensively explored as an important class of the essential polymers for various applications. In recent years, significant efforts have been made on the development of self-healable PU materials that possess high performance, extended lifetime, great reliability, and recyclability. A promising approach is the incorporation of covalent dynamic bonds into the design of PU covalently crosslinked polymers and thermoplastic elastomers that can dissociate and reform indefinitely in response to external stimuli or autonomously. This review summarizes various strategies to synthesize self-healable, reprocessable, and recyclable PU materials integrated with dynamic (reversible) Diels-Alder cycloadduct, disulfide, diselenide, imine, boronic ester, and hindered urea bond. Furthermore, various approaches utilizing the combination of dynamic covalent chemistries with nanofiller surface chemistries are described for the fabrication of dynamic heterogeneous PU composites.

Macromolecularly Engineered Thermoreversible Heterogeneous Self-Healable Networks Encapsulating Reactive Multidentate Block Copolymer-Stabilized Carbon Nanotubes.

The development of heterogeneous covalent adaptable networks (CANs) embedded with carbon nanotubes (CNTs) that undergo reversible dissociation/recombination through thermoreversibility has been significantly explored. However, the carbon nanotube (CNT)-incorporation methods based on physical mixing and chemical modification could result in either phase separation due to structural incompatibility or degrading conjugation due to a disruption of π-network, thus lowering their intrinsic charge transport properties. To address this issue, the versatility of a macromolecular engineering approach through thermoreversibility by physical modification of CNT surfaces with reactive multidentate block copolymers (rMDBCs) is demonstrated. The formed CNTs stabilized with rMDBCs (termed rMDBC/CNT colloids) bearing reactive furfuryl groups is functioned as a multicrosslinker that reacts with a polymaleimide to fabricate robust heterogeneous polyurethane (PU) networks crosslinked through dynamic Diels-Alder (DA)/retro-DA chemistry. Promisingly, the fabricated PU network gels in which CNTs through rMDBC covalently embedded are flexible and robust to be bendable as well as exhibit self-healing elasticity and enhanced conductivity.

Self-Healable Reprocessable Triboelectric Nanogenerators Fabricated with Vitrimeric Poly(hindered Urea) Networks.

In recent years, the advent of highly deformable and healable electronics is exciting and promising for next-generation electronic devices. In particular, self-healable triboelectric nanogenerators (SH-TENGs) serve as promising candidates based on the combination of the triboelectric effect, electrostatic induction, and self-healing action. However, the majority of SH-TENGs have been devised with weak polymeric networks that are healed with reversible supramolecular interactions or disulfides, thus resulting in poor mechanical properties and low resistance to creeping. To address this issue, we demonstrate the integration of mechanically strong and self-healable poly(hindered urea) (PHU) network in the fabrication of effective TENGs. The designed PHU network is flexible but shows greater mechanical property of tensile strength as high as 1.7 MPa at break. The network is capable of self-healing quickly and repeatedly as well as being reprocessable under mild conditions, enabling the recovery of triboelectric performances after the complete healing of the damaged surfaces. Furthermore, the interfacial-polarization-induced enhancement of dielectric constant endows our SH-TENG with the highest triboelectric output performance (169.9 V/cm2) among the reported healable TENGs. This work presents an avenue to the development of mechanical energy-harvesting devices and self-powered sensors with excellent stretchability, high recoverability, and good mechanical strength.

Poly(ionic liquid) embedded particles as efficient solid phase microextraction phases of polar and aromatic analytes.

In this work, a facile preparation of SPME fibers with increased surface area is presented. The SPME fibers were prepared by grinding poly(ionic liquids) (PILs) to obtain particles of 1-16 µm and, with the aid of a silicon adhesive, attach these particles to a steel wire support. Three different PILs, poly(1-vinyl-3-benzylimidazolium-co-styrene bromide) [poly(ViBnIm-co-Sty Br)], poly(1-vinyl-3-benzylimidazolium-co-styrene bis(trifluoromethanesulfonyl)imide) [poly(ViBnIm-co-Sty TFSI)] and poly(diallyldimethylamine bis(trifluoromethanesulfonyl)imide) [poly(Pyrr11 TFSI)], were used. The first two PILs were obtained by reversible addition-fragmentation chain transfer polymerization followed by metathesis reactions. The thicknesses of the prepared fibers were found to be 19 ±â€¯4 µm and 85% of the particles used have diameters between 2 and 10 µm. The prepared fibers were tested by performing the headspace extraction of two standard solutions, one containing a mixture of alcohols with different chain lengths, and the other a mixture of aromatic compounds, leading to sorption times of 10 - 15 min due the large surface area attained with this method. PILs with aromatic moieties containing the bromide anion showed high selectivity towards polar compounds, due to the hydrogen basicity of the anion, and also towards aromatic analytes, due to the aromatic nature of styrene moieties and the cation pendant groups. The limits of detection fall in the sub ppb level, while relative standard deviations and reproducibility from fiber-to-fiber found maximums of 16.2% and 22.5%, respectively. Furthermore, the PIL based fibers showed up to 90% higher extraction efficiencies compared to the commercial fibers of polydimethylsiloxane and polyacrylate.