Tough and fatigue-resistant polymer networks by crack tip softening.

Soft materials fail by crack propagation under external loads. While fracture toughness of a soft material can be enhanced by orders of magnitude, its fatigue threshold remains insusceptible. In this work, we demonstrate a crack tip softening (CTS) concept to simultaneously improve the toughness and threshold of a single polymeric network. Polyacrylamide hydrogels have been selected as a model material. The polymer network is cured by two kinds of crosslinkers: a normal crosslinker and a light-degradable crosslinker. We characterize the pristine sample and light-treated sample by shear modulus, fracture toughness, fatigue threshold, and fractocohesive length. Notably, we apply light at the crack tip of a sample so that the light-sensitive crosslinkers degrade, resulting in a CTS sample with a softer and elastic crack tip. The pristine sample has a fracture toughness of 748.3 ± 15.19 J/m2 and a fatigue threshold of 9.3 J/m2. By comparison, the CTS sample has a fracture toughness of 2,774.6 ± 127.14 J/m2 and a fatigue threshold of 33.8 J/m2. Both fracture toughness and fatigue threshold have been enhanced by about four times. We attribute this simultaneous enhancement to stress de-concentration and elastic shielding at the crack tip. Different from the "fiber/matrix composite" concept and the "crystallization at the crack tip" concept, the CTS concept in the present work provides another option to simultaneously enhance the toughness and threshold, which improves the reliability of soft devices during applications.

Microstructured Polyelectrolyte Elastomer-Based Ionotronic Sensors with High Sensitivities and Excellent Stability for Artificial Skins.

High-performance flexible pressure sensors are highly demanded for artificial tactile sensing. Using ionic conductors as the dielectric layer has enabled ionotronic pressure sensors with high sensitivities owing to giant capacitance of the electric double layer (EDL) formed at the ionic conductor/electronic conductor interface. However, conventional ionotronic sensors suffer from leakage, which greatly hinders long-term stability and practical applications. Herein, a leakage-free polyelectrolyte elastomer as the dielectric layer for ionotronic sensors is synthesized. The mechanical and electrical properties of the polyelectrolyte elastomer are optimized, a micropyramid array is constructed, and it is used as the dielectric layer for an ionotronic pressure sensor with marked performances. The obtained sensor exhibits a sensitivity of 69.6 kPa-1 , a high upper detecting limit on the order of 1 MPa, a fast response/recovery speed of ≈6 ms, and excellent stability under both static and dynamic loads. Notably, the sensor retains a high sensitivity of 4.96 kPa-1 at 500 kPa, and its broad sensing range within high-pressure realm enables a brand-new coding strategy. The applications of the sensor as a wearable keyboard and a quasicontinuous controller for a robotic arm are demonstrated. Durable and highly sensitive ionotronic sensors potentialize high-performance artificial skins for soft robots, human-machine interfaces, and beyond.

3D Printing of Conductive Hydrogel-Elastomer Hybrids for Stretchable Electronics.

Electronically conductive hydrogels integrated with dielectric elastomers show great promise in a wide range of applications, such as biomedical devices, soft robotics, and stretchable electronics. However, one big conundrum that impedes the functionality and performance of hydrogel-elastomer-based devices lies in the strict demands of device integration and the requirements for devices with satisfactory mechanical and electrical properties. Herein, the digital light processing three-dimensional (3D) printing method is used to fabricate 3D functional devices that bridge submillimeter-scale device resolution to centimeter-scale object size and simultaneously realize complex hybrid structures with strong adhesion interfaces and desired functionalities. The interconnected poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) network endows the PAAm hydrogel with high conductivity and superior electrical stability and poly(2-hydroxyethyl acrylate) functions as an insulating medium. The strong interfacial bonding between the hydrogel and elastomer is achieved by incomplete photopolymerization that ensures the stability of the hybrid structure. Lastly, applications of stretchable electronics illustrated as 3D-printed electroluminescent devices and 3D-printed capacitive sensors are conceptually demonstrated. This strategy will open up avenues to fabricate conductive hydrogel-elastomer hybrids in next-generation multifunctional stretchable electronics.

3D Printing Method for Tough Multifunctional Particle-Based Double-Network Hydrogels.

3D printing of hydrogels finds widespread applications in biomedicine and engineering. Artificial cartilages and heart valves, tissue regeneration and soft robots, require high mechanical performance of complex structures. Although many tough hydrogels have been developed, complicated synthesis processes hinder their fabrication in 3D printing. Here, a strategy is proposed to formulate hydrogel inks, which can be printed into various strong and tough particle-based double-network (P-DN) hydrogels of arbitrary shapes without any rheological modifiers. These hydrogel inks consist of microgels and a hydrogel precursor. The microgels are individual highly cross-linked networks. They are prepared by swelling dried microparticles in the hydrogel precursor that consists of monomers, initiators, and cross-linkers. Microgels regulate the rheological properties of the hydrogel ink and enable the direct printing. After printing and curing, the precursor forms a sparsely cross-linked network that integrates the microgels, leading to a P-DN hydrogel. The proposed hydrogel inks allow 3D printing of multifunctional hydrogel structures with high mechanical performance and strong adhesion to diverse materials. This strategy will open new avenues to fabricate multifunctional devices in tissue engineering and soft robotics.