Creep-free polyelectrolyte elastomer for drift-free iontronic sensing.

Artificial pressure sensors often use soft materials to achieve skin-like softness, but the viscoelastic creep of soft materials and the ion leakage, specifically for ionic conductors, cause signal drift and inaccurate measurement. Here we report drift-free iontronic sensing by designing and copolymerizing a leakage-free and creep-free polyelectrolyte elastomer containing two types of segments: charged segments having fixed cations to prevent ion leakage and neutral slippery segments with a high crosslink density for low creep. We show that an iontronic sensor using the polyelectrolyte elastomer barely drifts under an ultrahigh static pressure of 500 kPa (close to its Young's modulus), exhibits a drift rate two to three orders of magnitude lower than that of the sensors adopting conventional ionic conductors and enables steady and accurate control for robotic manipulation. Such drift-free iontronic sensing represents a step towards highly accurate sensing in robotics and beyond.

Experimental characterization of elastocapillary and osmocapillary effects on multi-scale gel surface topography.

Surface topography significantly affects various surface properties of polymer gels. Unlike conventional materials where surface topography is largely a geometric property, the surface topography of a polymer gel is governed by the competition between capillary, elastic, and osmotic effects, which leads to complex stimuli-responsive effects. Elastocapillary deformation and osmocapillary phase separation are two phenomena that are known to flatten gel surface topography. Here we experimentally quantify how osmocapillary phase separation affects gel surface topography by fabricating ionogels with multi-scale topography and characterizing the swelling-dependent surface flattening. Our observation confirms the vital role of the osmocapillary length in governing the surface behavior of swollen ionogels. This study provides the first quantitative experimental verification of the osmocapillary phase separation and shows the insufficiency of the previous studies based on elastocapillary deformation alone.

Encapsulating eutectogels for stretchable humidity-resistant strain sensors.

Eutectogels are stretchable ionic conductors extensively developed in recent years, owing to their distinct advantages of low cost, non-volatility, non-toxicity, and outstanding biocompatibility. However, the susceptibility to humidity caused by the exchange of water molecules between the interiors of eutectogels and the external environment greatly restricts their practical applications. Here, a dip-coating strategy is proposed to fabricate a P(MEA-co-IBA) elastomer-coated P(AAC-co-AAM) eutectogel to achieve satisfactory humidity-resistant capability. The hydrophobic elastomer coating significantly suppresses water exchange without harming the stretchability (>500%) and conductivity of the eutectogel. Strong adhesion forms at the eutectogel-coating interface due to the formation of an interpenetrating layer. The superior electromechanical performances of encapsulated eutectogels enable stretchable ionotronic devices with stable electrical performance (>1 h) and remarkable water-droplet/moist resistances during static/dynamic loadings. A humidity-resistant encapsulated eutectogel-based wearable strain sensor is further demonstrated. The proposed humidity-resistant eutectogels are promising candidates for soft and wearable ionotronics for practical applications.

Progress of Hydrophobic Ionogels: A Review.

The emergence of hydrophobic ionogels composed of hydrophobic polymer matrices and hydrophobic ionic liquids has drastically broadened the applications of ionic devices, especially for underwater explorations. Compared with traditional ionogels, hydrophobic ones are capable of achieving long-term stability in ambient and aqueous environments. In this review, the latest research developments of intrinsically hydrophobic ionogels are summarized, with particular emphases placed on the materials, mechanisms and applications. The basic issues about hydrophobic ionogels, including the material systems, dynamic gelation bonds and network structures are elucidated. The up-to-date advent of the ambient/underwater applications of hydrophobic ionogels concerning adhesion, self-healing, and sensing are comprehensively summarized. Special attention is paid to underwater scenarios considering the rapid development of marine explorations and the intrinsic properties of hydrophobic ionogels. Finally, the current challenges and immediate opportunities of this emerging yet fast-developing research field are discussed.

Harnessing osmotic swelling stress for robust hydrogel actuators.

The volumetric expansion of hydrogels driven by osmotic swelling stress has enabled hydrogel actuators for myriad applications. However, most existing studies disregard optimizing the osmotic swelling stress for powerful actuation and simply utilize the osmotic swelling stress to trigger certain modes of actuation. In this work, we probe the osmotic swelling stress of hydrogels using polyacrylamide as a model system. We design and perform constrained swelling experiments to measure the osmotic swelling stresses at different levels of constraint and compare the results to the theoretical predictions based on the Flory-Huggins model. We optimize the osmotic swelling properties by tuning the constituents and structures of the hydrogel and achieve an enhancement of the magnitude of actuation stress from ∼180 kPa to ∼400 kPa. As a proof of concept, we demonstrate a robust hydrogel jack that can lift a weight 2000 times its own weight by harnessing the high osmotic swelling stress. The feasibility and limits of harnessing the osmotic swelling stress of hydrogels for actuation are discussed.

Simulation of the peel of hydrogels with stiff backing.

In this work, the peel of hydrogels under a stiff backing constraint was studied using a finite element method. The finite element method was first validated by comparing the simulation results to theoretical predictions and experimental measurements. Then, the method was used to investigate the effects of adhesion thickness, adhesion length and backing thickness on the peel behaviors, as well as the stress distribution within the adhesion layer. The results indicated that the peel force-displacement curve has a constant profile when the adhesion thickness and backing thickness are prescribed so long as the adhesion length is sufficiently long. The peak peel force increases with the adhesion length and then plateaus. The larger the intrinsic peak stress or the thicker the backing, the higher the plateau. The steady-state peel force is independent of the backing thickness, while positively correlated with the strain energy storage of the hydrogel adhesion layer. The critical vertical displacement corresponding to the peak peel force increases with the hydrogel thickness and decreases with the backing thickness. However, the critical vertical displacement corresponding to the steady-state peel force increases with the backing thickness. The present work puts forward an effective numerical approach to probe the peel of hydrogels, which is beneficial for the design of relevant structures.

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.

Polyelectrolyte elastomer-based ionotronic sensors with multi-mode sensing capabilities via multi-material 3D printing.

Stretchable ionotronics have drawn increasing attention during the past decade, enabling myriad applications in engineering and biomedicine. However, existing ionotronic sensors suffer from limited sensing capabilities due to simple device structures and poor stability due to the leakage of ingredients. In this study, we rationally design and fabricate a plethora of architected leakage-free ionotronic sensors with multi-mode sensing capabilities, using DLP-based 3D printing and a polyelectrolyte elastomer. We synthesize a photo-polymerizable ionic monomer for the polyelectrolyte elastomer, which is stretchable, transparent, ionically conductive, thermally stable, and leakage-resistant. The printed sensors possess robust interfaces and extraordinary long-term stability. The multi-material 3D printing allows high flexibility in structural design, enabling the sensing of tension, compression, shear, and torsion, with on-demand tailorable sensitivities through elaborate programming of device architectures. Furthermore, we fabricate integrated ionotronic sensors that can perceive different mechanical stimuli simultaneously without mutual signal interferences. We demonstrate a sensing kit consisting of four shear sensors and one compressive sensor, and connect it to a remote-control system that is programmed to wirelessly control the flight of a drone. Multi-material 3D printing of leakage-free polyelectrolyte elastomers paves new avenues for manufacturing stretchable ionotronics by resolving the deficiencies of stability and functionalities simultaneously.

Stretchable Heterogeneous Polymer Networks of High Adhesion and Low Hysteresis.

Adhesives are ubiquitous, but the mutual exclusion between hyperelasticity and adhesiveness impedes their uses in emerging techniques such as flexible/stretchable electronics. Herein, we propose a strategy to synthesize hyperelastic adhesives (HEAs), by designating hyperelasticity and adhesiveness to the bulk and the surface of a polymer network, respectively. The bulk is hyperelastic but nonadhesive, and the surface is viscoelastic but adhesive, while the HEA is hyperelastic and adhesive. We exemplify the principle by synthesizing poly(butyl acrylate) as the bulk and poly(butyl acrylate-co-isobornyl acrylate) as the surface. The resulting HEA exhibits a low hysteresis of 4% at 100% strain and an adhesion energy of 270 J m-2. Moreover, the HEA is optically transparent, thermally stable, spontaneously adhesive to various materials, and mechanically stable against cyclic load, relaxation, and creep. We demonstrate two applications enabled by the unique combination of hyperelasticity and adhesiveness. The proposed strategy is generic, paving new avenues for stretchable yet resilient adhesives for diverse applications.

Tough porous nanocomposite hydrogel for water treatment.

Developing a cost-effective, stable, and recyclable adsorbent with high adsorption capacity and rapid adsorption kinetics is highly demanded for water treatment but has been proven challenging. Herein, we report a one-step strategy to synthesize tough porous nanocomposite hydrogel, by introducing biochar nanoparticles and interconnected pores into a polyacrylamide hydrogel matrix as an exemplary system. The polyacrylamide hydrogel provides the overall mechanical strength to carry loads and facilitate recycling, the biochar provides adsorptive locus for high adsorption capacity, and the interconnected pores expedite solvent transport for rapid adsorption kinetics. Mechanical characterizations manifest that the porous biochar hydrogel possesses a tensile strength of 128 kPa, a stretchability of 5.9, and a toughness of 538 J m-2. Porous structure analysis reveals that the hydrogel contains an increscent specific surface area by 441% and an augmented pore volume by 279% compared to pure polyacrylamide hydrogel. Experiments pertaining to adsorption isotherms and kinetics, with methylene blue as the model adsorbate, indicate enhanced adsorption performances. The tough hydrogel also allows facile recycling and maintains mechanical robustness after five regeneration cycles. Furthermore, biocompatibility is endorsed by cytotoxicity test. The proposed method could open an ample space for designing and synthesizing tough porous nanocomposite hydrogels for water treatment.

Strong Interfaces Enable Efficient Load Transfer for Strong, Tough, and Impact-Resistant Hydrogel Composites.

Many biological hydrogels are mechanically robust to bear quasi-static and impact loads. In contrast, the mechanical properties of synthetic hydrogels against impact loads remain substantially unexplored, albeit their mechanical robustness under quasi-static loads has been extensively developed. Here, we report on the design and synthesis of strong, tough, and impact-resistant hydrogel composites by reinforcing Ca-alginate/polyacrylamide hydrogels with glass fabrics and conferring strong interfaces between the hydrogel matrix and the fibers. The fabric enables high elastic modulus, the hydrogel matrix enables large dissipation, and the strong interfaces enable efficient load transfer for synergistic strengthening and toughening, which is manifested by digital image correlation analyses. Under quasi-static loads, the hydrogel composite exhibits an elastic modulus of 35 MPa and a toughness of 206.7 kJ/m2. Under impact loads, a piece of 7.7 g sample bears the impact of energy of 7.4 J and resists more than 100 cycles of consecutive impact of 600 mJ. As a proof-of-concept, a hydrogel composite as a safeguard to protect fragile glasses from impact is demonstrated. Because impact phenomena are universal, it is expected that the study on the impact of hydrogels will draw increasing attention.

Highly stable flexible pressure sensors with a quasi-homogeneous composition and interlinked interfaces.

Electronic skins (e-skins) are devices that can respond to mechanical stimuli and enable robots to perceive their surroundings. A great challenge for existing e-skins is that they may easily fail under extreme mechanical conditions due to their multilayered architecture with mechanical mismatch and weak adhesion between the interlayers. Here we report a flexible pressure sensor with tough interfaces enabled by two strategies: quasi-homogeneous composition that ensures mechanical match of interlayers, and interlinked microconed interface that results in a high interfacial toughness of 390 J·m-2. The tough interface endows the sensor with exceptional signal stability determined by performing 100,000 cycles of rubbing, and fixing the sensor on a car tread and driving 2.6 km on an asphalt road. The topological interlinks can be further extended to soft robot-sensor integration, enabling a seamless interface between the sensor and robot for highly stable sensing performance during manipulation tasks under complicated mechanical conditions.

Fatigue Damage-Resistant Physical Hydrogel Adhesion.

Strong adhesion between hydrogels and various engineering surfaces has been achieved; yet, achieving fatigue-resistant hydrogel adhesion remains challenging. Here, we examine the fatigue of a specific type of hydrogel adhesion enabled by hydrogen bonds and wrinkling and show that the physical interactions-based hydrogel adhesion can resist fatigue damage. We synthesize polyacrylamide hydrogel as the adherend and poly(acrylic acid-co-acrylamide) hydrogel as the adhesive. The adherend and the adhesive interact via hydrogen bonds. We further introduce wrinkles at the interface by biaxially prestretching and then releasing the adherends and perform butt-joint tests to probe the adhesion performance. Experimental results reveal that the samples with a wrinkled interface resist fatigue damage, while the samples with a flat interface fail in ~9,000 cycles at stress levels of 70 and 63% peak stresses in static failure. The endurance limit of the wrinkled-interface samples is comparable to the peak stress of the flat-interface samples. Moreover, we find that the nearly perfectly elastic polyacrylamide hydrogel also suffers fatigue damage, which limits the fatigue life of the wrinkled-interface samples. When cohesive failure ensues, the evolutions of the elastic modulus of wrinkled-interface samples and hydrogel bulk, both in satisfactory agreements with the predictions of damage accumulation theory, are alike. We observe similar behaviors in different material systems with polyacrylamide hydrogels with different water contents. This work proves that physical interactions can be engaged in engineering fatigue-resistant adhesion between soft materials such as hydrogels.

Direct-ink-write printing of hydrogels using dilute inks.

Direct-ink-write (DIW) printing has been used in myriad applications. Existing DIW printing relies on inks of specific rheology to compromise with printing process, imposing restrictions on the choice of printable materials. Reported ink viscosity ranges from 10-1 to 103 Pa·s. Here we report a method to enable DIW printing that is compatible with dilute ink (10-3 Pa·s) by manipulating the interactions between ink and substrate. By exemplifying hydrogel printing, we build a printing system and show that dilute ink of appropriate surface energy, once extruded, can spontaneously wet and reside within the region of higher surface energy on a substrate of lower surface energy, while resisting gravity and maintaining shape before solidification. We demonstrate the diversity for printing various materials on various substrates and three deployments immediately enabled by the proposed method. The method expands the range of printable materials for DIW printing and the toolbox for additive manufacturing.

Ionotronic Luminescent Fibers, Fabrics, and Other Configurations.

A family of recently developed devices, hydrogel ionotronics, uses hydrogels as ionic conductors, and uses hydrophobic elastomers as dielectrics. This development has posed a challenge: integrate hydrogels and hydrophobic elastomers-in various manufacturing processes-with strong, stretchable, and transparent adhesion. Here, a multistep dip-coating process is described to enable hydrogel ionotronics of diverse configurations. In doing so, a hydrophobic surface is primed to let a hydrophilic precursor wet it, and then polymers of different layers are interlinked with covalent bonds. As a representative example, an ionotronic luminescent fiber that can be lengthened to ≈2.5 times its original length and keeps functioning after 10 000 cycles of stretching is fabricated. A luminescent fabric that displays movable pixels and other configurations is also demonstrated. The proposed method of fabrication expands the design space for hydrogel ionotronics.

Hydrogel Paint.

For a hydrogel coating on a substrate to be stable, covalent bonds polymerize monomer units into polymer chains, crosslink the polymer chains into a polymer network, and interlink the polymer network to the substrate. The three processes-polymerization, crosslinking, and interlinking-usually concur. This concurrency hinders widespread applications of hydrogel coatings. Here a principle is described to create hydrogel paints that decouple polymerization from crosslinking and interlinking. Like a common paint, a hydrogel paint divides the labor between the paint maker and the paint user. The paint maker formulates the hydrogel paint by copolymerizing monomer units and coupling agents into polymer chains, but does not crosslink them. The paint user applies the paint on various materials (elastomer, plastic, glass, ceramic, or metal), and by various operations (brush, cast, dip, spin, or spray). During cure, the coupling agents crosslink the polymer chains into a network and interlink the polymer network to the substrate. As an example, hydrogels with thickness in the range of 2-20 µm are dip coated on medical nitinol wires. The coated wires reduce friction by eightfold, and remain stable over 50 test cycles. Also demonstrated are several proof-of-concept applications, including stimuli-responsive structures and antifouling model boats.

Design Molecular Topology for Wet-Dry Adhesion.

Recent innovations highlight the integration of diverse materials with synthetic and biological hydrogels. Examples include brain-machine interfaces, tissue regeneration, and soft ionic devices. Existing methods of strong adhesion mostly focus on the chemistry of bonds and the mechanics of dissipation but largely overlook the molecular topology of connection. Here, we highlight the significance of molecular topology by designing a specific bond-stitch topology. The bond-stitch topology achieves strong adhesion between preformed hydrogels and various materials, where the hydrogels have no functional groups for chemical coupling, and the adhered materials have functional groups on the surface. The adhesion principle requires a species of polymer chains to form a bond with a material through complementary functional groups and form a network in situ that stitches with the polymer network of a hydrogel. We study the physics and chemistry of this topology and describe its potential applications in medicine and engineering.

[Effect of ursolic acid on proliferation and apoptosis of hepatic stellate cells in vitro].

OBJECTIVE: To investigate the effect of ursolic acid on proliferation and apoptosis of hepatic stellate cells (HSC) in vitro and explore the mechanisms of apoptosis of HSC induced by ursolic acid by studying the expressions of apoptosis-regulating proteins Bcl-2, Bax and Caspase 3 in HSC. METHODS: Hepatic stellate cells HSC-T6 and hepatocytes L02 were incubated with different concentrations of ursolic acid (25, 50, 75, 100, 125 and 150 micromol/L) for 24 h, 48 h and 72 h. The effect of ursolic acid on the cell proliferation was studied by methyl thiazolyl tetrazolium (MTT) colorimetric assay. The rate of HSC-T6 apoptosis was identified by flow cytometry (FCM) and the morphological change of apoptosis was observed with light microscopy. The expressions of apoptosis-regulating protein Bcl-2, Bax and Caspase 3 in HSC-T6 after apoptosis induced by ursolic acid were examined by immunocytochemical staining assay. RESULTS: MTT analysis indicated administration of 25-150 micromol/L ursolic acid incubated with HSC-T6 for 24 h, 48 h and 72 h significantly inhibited HSC-T6 proliferation in a dose-dependent and time-dependent manner compared with the control group. Promotive effect of ursolic acid on proliferation of hepatocyte L02 was observed in the 25, 50, 75 micromol/L concentration groups. Ursolic acid inhibited L02 proliferation when its concentration was higher than 100 micromol/L and for 72 hours or longer. HE stained histological slides demonstrated morphologic changes of HSC-T6, including karyorrhexis and cytoplasm vacuolization, when they were treated with ursolic acid at 75 micromol/L concentrations for 48 h. FCM showed the apoptosis ratios of HSC-T6 were 10.30%+/-3.85%, 21.87%+/-4.46% and 31.33%+/-6.18% after treating HSC-T6 with ursolic acid at concentrations of 25, 50 and 75 micromol/L for 48 h. They were significantly higher than that of the control group 2.93%+/-1.60%. Immunocytochemistry also indicated the expressions of Bax and caspase 3 protein in HSC-T6 cells were up-regulated in a dose-dependent manner, but expressions of Bcl-2 protein were not significantly different from that of the blank control group (P more than 0.05). CONCLUSIONS: Ursolic acid could significantly inhibit HSC proliferation and induce apoptosis in a dose-dependent and time-dependent manner. Ursolic acid in low concentration promotes proliferation of L02 cells, but in high concentrations (more than 100 micromol/L) it inhibits the growth of hepatocytes. Expressions of Bax and Caspase 3 in apoptotic HSC were increased; expressions of Bcl-2 protein were not significantly different from that of the control group, while Bcl-2/Bax ratio was reduced. Our results suggest that HSC-T6 cell apoptosis induced by ursolic acid occurs through mechanisms involving mitochondrial pathways and Bcl-2 family proteins.

Bonding dissimilar polymer networks in various manufacturing processes.

Recently developed devices mimic neuromuscular and neurosensory systems by integrating hydrogels and hydrophobic elastomers. While different methods are developed to bond hydrogels with hydrophobic elastomers, it remains a challenge to coat and print various hydrogels and elastomers of arbitrary shapes, in arbitrary sequences, with strong adhesion. Here we report an approach to meet this challenge. We mix silane coupling agents into the precursors of the networks, and tune the kinetics such that, when the networks form, the coupling agents incorporate into the polymer chains, but do not condensate. After a manufacturing step, the coupling agents condensate, add crosslinks inside the networks, and form bonds between the networks. This approach enables independent bonding and manufacturing. We formulate oxygen-tolerant hydrogel resins for spinning, printing, and coating in the open air. We find that thin elastomer coatings enable hydrogels to sustain high temperatures without boiling.

Fatigue Fracture of Self-Recovery Hydrogels.

Hydrogels of superior mechanical behavior are under intense development for many applications. Some of these hydrogels can recover their stress-stretch curves after many loading cycles. These hydrogels are called self-recovery hydrogels or even fatigue-free hydrogels. Such a hydrogel typically contains a covalent polymer network, together with some noncovalent, reversible interactions. Here we show that self-recovery hydrogels are still susceptible to fatigue fracture. We study a hydrogel containing both covalently cross-linked polyacrylamide and un-cross-linked poly(vinyl alcohol). For a sample without precut crack, the stress-stretch curve recovers after thousands of loading cycles. For a sample with a precut crack, however, the crack extends cycle by cycle. The threshold for fatigue fracture depends on the covalent network but negligibly on noncovalent interactions. Above the threshold, the noncovalent interactions slow down the extension of the crack under cyclic loads.