ABSTRACT
Despite the intensive research in room-temperature phosphorescent (RTP) polymers, the synthesis of RTP polymers with well-defined macromolecular structures and multiple functions remains a challenge. Herein, reversible deactivation radical polymerization was demonstrated to offer a gradient copolymer (GCP) architecture with controlled heterogeneities, which combines hard segment and flexible segment. The GCPs would self-assemble into a multiphase nanostructure, featuring tunable stretchability, excellent RTP performance, and intrinsic healability without compromising light emission under stretching. The mechanical performance is tunable on demand with elongation at break ranging from 5.0% to 221.7% and Young's modulus ranging from 0.5 to 225.0 MPa.
ABSTRACT
Organic mechanophores have been widely adopted for polymer mechanotransduction. However, most examples of polymer mechanotransduction inevitably experience macromolecular chain rupture, and few of them mimic mussel's mechanochemical regeneration, a mechanically mediated process from functional units to functional materials in a controlled manner. In this paper, inorganic mechanoluminescent (ML) materials composed of CaZnOS-ZnS-SrZnOS: Mn2+ were used as a mechanotransducer since it features both piezoelectricity and mechanolunimescence. The utilization of ML materials in polymerization enables both mechanochemically controlled radical polymerization and the synthesis of ML polymer composites. This procedure features a mechanochemically controlled manner for the design and synthesis of diverse mechanoresponsive polymer composites.
ABSTRACT
Traditional mechanochemically controlled reversible-deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high-energy and high-frequency stimuli. Here, we propose a facile approach for tribochemically controlled atom transfer radical polymerization (tribo-ATRP) that relies on contact-electro-catalysis (CEC) between titanium oxide (TiO2 ) particles and CuBr2 /tris(2-pyridylmethylamine (TPMA), without any high-energy input. Under the friction induced by stirring, the TiO2 particles are electrified, continuously reducing CuBr2 /TPMA into CuBr/TPMA, thereby conversing alkyl halides into active radicals to start ATRP. In addition, the effect of friction on the reaction was elucidated by theoretical simulation. The results indicated that increasing the frequency could reduce the energy barrier for the electron transfer from TiO2 particles to CuBr2 /TPMA. In this study, the design of tribo-ATRP was successfully achieved, enabling CEC (ca. 10â Hz) access to a variety of polymers with predetermined molecular weights, low dispersity, and high chain-end fidelity.
ABSTRACT
High-quality and free-standing polyimide (PI) film with desirable mechanical properties and uniformity is in high demand due to its widespread applications in highly precise flexible and chip-integrated sensors. In this study, a free-standing PI film with high toughness was successfully prepared using a diamine monomer with ether linkages. The prepared PI films exhibited significantly superior mechanical properties compared to PI films of the same molecular structure, which can be attributed to the systematic exploration of the film-forming process. The exploration of the film-forming process includes the curing procedures, film-forming substrates, and annealing treatments. Additionally, the thickness uniformity and surface homogeneity of free-standing films were crucial for toughness. Increasing the crystallinity of the PI films by eliminating residual stress also contributed to their high strength. The results demonstrate that by adjusting the above-mentioned factors, the prepared PI films possess excellent mechanical properties, with tensile strength and elongation at break of 194.71 MPa and 130.13%, respectively.
ABSTRACT
Synthesis of large-area patterned MoS2 is considered the principle base for realizing high-performance MoS2 -based flexible electronic devices. Patterning and transferring MoS2 films to target flexible substrates, however, require conventional multi-step photolithography patterning and transferring process, despite tremendous progress in the facilitation of practical applications. Herein, an approach to directly synthesize large-scale MoS2 patterns that combines inkjet printing and thermal annealing is reported. An optimal precursor ink is prepared that can deposit arbitrary patterns on polyimide films. By introducing a gas atmosphere of argon/hydrogen (Ar/H2 ), thermal treatment at 350 °C enables an in situ decomposition and crystallization in the patterned precursors and, consequently, results in the formation of MoS2 . Without complicated processes, patterned MoS2 is obtained directly on polymer substrate, exhibiting superior mechanical flexibility and durability (≈2% variation in resistance over 10,000 bending cycles), as well as excellent chemical stability, which is attributed to the generated continuous and thin microstructures, as well as their strong adhesion with the substrate. As a step further, this approach is employed to manufacture various flexible sensing devices that are insensitive to body motions and moisture, including temperature sensors and biopotential sensing systems for real-time, continuously monitoring skin temperature, electrocardiography, and electromyography signals.
