Tough Hydrogels Research Articles

Tough Hydrogels for Load-Bearing Applications.

Tough hydrogels have emerged as a promising class of materials to target load-bearing applications, where the material has to resist multiple cycles of extreme mechanical impact. A variety of chemical interactions and network architectures are used to enhance the mechanical properties and fracture mechanics of hydrogels making them stiffer and tougher. In recent years, the mechanical properties of tough, high-performance hydrogels have been benchmarked, however, this is often incomplete as important variables like water content are largely ignored. In this review, the aim is to clarify the reported mechanical properties of state-of-the-art tough hydrogels by providing a comprehensive library of fracture and mechanical property data. First, common methods for mechanical characterization of such high-performance hydrogels are introduced. Then, various modes of energy dissipation to obtain tough hydrogels are discussed and used to categorize the individual datasets helping to asses the material's (fracture) mechanical properties. Finally, current applications are considered, tough high-performance hydrogels are compared with existing materials, and promising future opportunities are discussed.

Stretchable and tough polystyrene hydrogels by introducing polyacrylamide network

Stretchable and tough polystyrene hydrogels by introducing polyacrylamide network

Triple-Mechanism Enhanced Flexible SiO2 Nanofiber Composite Hydrogel with High Stiffness and Toughness for Cartilaginous Ligaments.

Hydrogels are widely used in tissue engineering, soft robotics and wearable electronics. However, it is difficult to achieve both the required toughness and stiffness, which severely hampers their application as load-bearing materials. This study presents a strategy to develop a hard and tough composite hydrogel. Herein, flexible SiO2 nanofibers (SNF) are dispersed homogeneously in a polyvinyl alcohol (PVA) matrix using the synergistic effect of freeze-drying and annealing through the phase separation, the modulation of macromolecular chain movement and the promotion of macromolecular crystallization. When the stress is applied, the strong molecular interaction between PVA and SNF effectively disperses the load damage to the substrate. Freeze-dried and annealed-flexible SiO2 nanofibers/polyvinyl alcohol (FDA-SNF/PVA) reaches a preferred balance between enhanced stiffness (13.71 ± 0.28MPa) and toughness (9.9 ± 0.4MJ m-3). Besides, FDA-SNF/PVA hydrogel has a high tensile strength of 7.84 ± 0.10MPa, super elasticity (no plastic deformation under 100 cycles of stretching), fast deformation recovery ability and excellent mechanical properties that are superior to the other tough PVA hydrogels, providing an effective way to optimize the mechanical properties of hydrogels for potential applications in artificial tendons and ligaments.

Extrusion bioprinting of elastin‐containing bioactive double‐network tough hydrogels for complex elastic tissue regeneration

AbstractDespite recent advances in extrusion bioprinting of cell‐laden hydrogels, using naturally derived bioinks to biofabricate complex elastic tissues with both satisfying biological functionalities and superior mechanical properties is hitherto an unmet challenge. Here, we address this challenge with precisely designed biological tough hydrogel bioinks featuring a double‐network structure. The tough hydrogels consisted of energy‐dissipative dynamically crosslinked glycosaminoglycan hyaluronic acid (o‐nitrobenzyl‐grafted hyaluronic acid) and elastin through Schiff's base reaction, and free‐radically polymerized gelatin methacryloyl. The incorporation of elastin further improved the elasticity, stretchability (∼170% strain), and toughness (∼45 kJ m−3) of the hydrogels due to the random coiling structure. We used this novel class of hydrogel bioinks to bioprint several complex elastic tissues with good shape retention. Furthermore, in vitro and in vivo experiments also demonstrated that the existence of elastin in the biocompatible bioinks facilitated improved cell behaviors and biological functions of bioprinted tissues, such as cell spreading and phenotype maintenance as well as tissue regeneration. The results confirmed the potential of the elastin‐containing tough hydrogel bioinks for bioprinting of 3D complex elastic tissues with biological functionalities, which may find widespread applications in elastic tissue regeneration.

Tough supramolecular hydrogels of poly(N,N-dimethylacrylamide)-grafted poly(methacrylic acid) with cooperative hydrogen bonds as physical crosslinks.

Incorporating associative interactions as the energy dissipation units has been recognized as an effective strategy to develop tough hydrogels. For hydrogen-bond associations, however, it is highly challenging to stabilize them under aqueous conditions. Although affording cooperativity can enhance and stabilize the hydrogen bonds, it usually requires stepwise polymerization to form these cooperative associations between different polymers and networks. Here, we report a series of tough supramolecular hydrogels with robust hydrogen-bond associations between grafted polymers that are synthesized by polymerization of a macromonomer of poly(N,N-dimethylacrylamide) (PDMAA) and a small monomer of methacrylic acid. The grafted chains of PDMAA form cooperative hydrogen bonds with the main chain of poly(methacrylic acid) (PMAAc), forming supramolecular hydrogels with high toughness and good stability. The tough and stiff hydrogels are in a glassy state, exhibit forced elastic deformation at room temperature, and remain stable over a wide pH range. In contrast, hydrogels prepared by the copolymerization of DMAA and MAAc are swollen and weak in water due to the lack of successive hydrogen donor/acceptor units and the absence of cooperative hydrogen bonds. In addition, these tough hydrogels exhibit good recyclability and shape memory properties, owing to the supramolecular nature of the network and the temperature-dependent mechanical properties. The influence of polymer structure on the associative interactions and macroscopic properties of the hydrogels should be informative for the design of tough soft materials with versatile applications.

Strong, tough and conductive single-network hydrogels based on deswelling and the salting-out effect.

In recent years, the continuous attention given to increasing the fracture toughness and Young's modulus of polymeric gels has gradually shifted from toughening strategies on double-network (DN) gels to single-network (SN) gels. The salt-soaking method has been adopted to realize the toughening of SN gels through the salting-out effect and deswelling, constructing dense network structures with simultaneously precipitated polymer chains and cross-links. By comparing the mechanical properties between salt-treated hydrogels and air-dried hydrogels, the increased polymer chain concentration is proved to promote energy transfer by enlarging the dissipation region size due to the unwinding and slippage of coiled chains during stretching. The newly formed cross-link points in salt-treated hydrogels are considered to consume more deformation energy during stretching. The synergistic effect in energy transfer and dissipation arising from increases in polymer fraction and cross-linking plays an indispensable role in toughening SN hydrogels. In addition, the soaking process introduces abundant free ions to endow hydrogels with prominent conductivity. Thus, this salt-soaking method provides a general approach to synthesize strong, tough and conductive hydrogels with applications in flexible electrical devices.

Elastic and conductive gellan gum/polyvinyl alcohol physical hydrogels with low swelling potential for sustainable flexible electronics

Conductive hydrogels are considered to be promising materials for flexible electronics, but those nondegradable are bound to produce substantial undesirable electronic wastes once widely applied, inconsistent with the long-term sustainable development goals. To develop biodegradable conductive hydrogels for sustainable flexible electronics, a green chemical reaction-free strategy was developed to manufacture a novel type of composite hydrogels, exploiting biodegradable gellan gum and polyvinyl alcohol as the matrices and natural-derived tannic acid as the crosslinking agent. The technique involves successive cool-induced sol−gel transition, freeze-thawing and Na2SO4 solution treatment. A universal electronic testing machine, scanning electronic microscope, X-ray diffractometer, thermogravimetric analyzer, and electrochemical work station were employed to study the mechanics, structure and morphology, swelling and conductivity of the hydrogels. The results indicate strong, elastic and tough hydrogels were achieved owing to the multi-crosslinked multiple-network structure. The maximum compressive stress (90% strain), tensile strength, breakage elongation and fracture energy reach 10.7 MPa, 1.2 MPa, 890% and 480 kJ/m3 respectively. The stress recovery rate still remains 86% after 10 consecutive loading-unloading under 200% strain. The highest conductivity reaches 3.27 S/m, which along with the excellent mechanics confers them good strain-sensing behavior. Moreover, the final hydrogels show low swelling in both water (the equilibrium swelling ratio (ESR) < 300%) and physiological saline (ESR < 90%). The excellent mechanical performance, high conductivity and good strain sensing, low swelling and inherent biodegradability as well as the ecofriendly manufacturing process imply potential prospect in sustainable flexible electronics.

A tough, anti-freezing, and low-dehydration rate gelatin hydrogel with inverse temperature-dependent ionic conductivity

By using Cit3− and Cl− salts together in a gelatin hydrogel, an inverse temperature-dependent ionic conductivity behavior was observed. The developed hydrogel II exhibited excellent mechanical toughness, freezing tolerance and low dehydration rate.

Engineering stiff and tough protein-based hydrogels: Bridging the mechanical gap between muscle and cartilage

Engineering stiff and tough protein-based hydrogels: Bridging the mechanical gap between muscle and cartilage

A tough and piezoelectric poly(acrylamide/N,N-dimethylacrylamide) hydrogel-based flexible wearable sensor.

A flexible, tough, highly transparent and piezoelectric polyacrylamide hydrogel was fabricated induced by blue light photocuring, with camphorquinone/diphenyliodonium hexafluorophosphate (CQ/DPI) as the blue light initiator, acrylamide (AM) and N,N-dimethylacrylamide (DMAA) as monomers, polyethylene glycol diacrylate (PEGDA) as the crosslinker, lecithin as the dispersant, and BaTiO3 as the piezoelectric material. Various performance tests were carried out on the hydrogel, and the results showed that lecithin enhances the dispersion of BaTiO3 within the system and improves the tensile properties (>100% strain) of the hydrogel, and the addition of PEGDA not only improves the photopolymerization performance of the hydrogel, but also significantly improves its fracture strength (∼0.3 MPa). In addition, BaTiO3 enables the resultant hydrogels to show excellent conductivity (>1.5) and stable response to strain. The assembled hydrogel sensor shows a sensitive response to human joint activities, which is expected to be applied in self-powered sensors and energy collection.

Tough and adhesive conductive hydrogels with fast gelation from a polyphenol–aluminium ion dual self-catalysis system for wearable strain sensors and triboelectric nanogenerators

A tough and adhesive conductive double network hydrogel (PVA/PHEAA–TA–Al3+ gel) was prepared via rapid in situ room temperature gelation processes (25 °C, 215 s) in a tannic acid–aluminium ion (TA–Al3+) dual self-catalysis system.

New insights into pure zwitterionic hydrogels with high strength and high toughness.

Zwitterionic hydrogels are electrically neutral materials with both cationic and anionic groups that impart excellent anti-fouling properties and ion channel orientations. However, pure zwitterionic hydrogels generally exhibit low strength and toughness. In this study, it has been discovered that polymerizable zwitterionic monomers in aqueous solution exhibit a unique liquid-liquid phase separation phenomenon at a high monomer concentration of ≥50 wt%, resulting in pure and commercial zwitterionic hydrogels with high compressive strength (6.5 MPa) and high toughness (2.12 kJ m-2). This phase separation and the corresponding aggregations might be caused by strong dipole-dipole interactions among residual zwitterionic monomers under the lack of free-water condition. The synergistic effect of liquid-liquid phase separation and polymer entanglement enhances the mechanical strength, toughness, self-recovery, and anti-freezing properties of pure polyzwitterionic hydrogels. Moreover, the high fracture energy of highly elongated yet tough polyzwitterionic hydrogels facilitates the development of high crack propagation resistance, which supports an expanded role in tissue engineering, soft flexible devices, and electronics applications with improved durability. A wide range of applications for the proposed polyzwitterionic hydrogels is demonstrated by the development and testing of a strain sensor and a triboelectric nanogenerator device. Our findings provide novel insights into the network structure of pure polyzwitterionic hydrogels.

Tough, self-healing and injectable dynamic nanocomposite hydrogel based on gelatin and sodium alginate

Biomacromolecules based injectable and self-healing hydrogels possessing high mechanical properties have widespread potential in biomedical field. However, dynamic features are usually inversely proportional to toughness. It is challenging to simultaneously endow these properties to the dynamic hydrogels. Here, we fabricated an injectable nanocomposite hydrogel (CS-NPs@OSA-l-Gtn) stimultaneously possessing excellent autonomous self-healing performance and high mechanical strength by doping chitosan nanoparticles (CS-NPs) into dynamic polymer networks of oxidized sodium alginate (OSA) and gelatin (Gtn) in the presence of borax. The synergistic effect of the multiple reversible interactions combining dynamic covalent bonds (i.e., imine bond and borate ester bond) and noncovalent interactions (i.e., electrostatic interaction and hydrogen bond) provide effective energy dissipation to endure high fatigue resistance and cyclic loading. The dynamic hydrogel exhibited excellent mechanical properties like maximum 2.43 MPa compressive strength, 493.91 % fracture strain, and 89.54 kJ/m3 toughness. Moreover, the integrated hydrogel after injection and self-healing could withstand 150 successive compressive cycles. Besides, the bovine serum albumin embedded in CS-NPs could be sustainably released from the nanocomposite hydrogel for 12 days. This study proposes a novel strategy to synthesize an injectable and self-healing hydrogel combined with excellent mechanical properties for designing high-strength natural carriers with sustained protein delivery.

Strong, tough, and elastic poly(vinyl alcohol)/polyacrylamide DN hydrogels based on the Hofmeister effect for articular cartilage replacement.

Traditional hydrogels are usually weak and brittle, which limit their application in articular cartilage replacement because cartilage is generally strong, tough, and elastic in nature. Therefore, it is highly desirable to construct hydrogels to mimic the mechanical properties of the native articular cartilage. Herein, in this work, poly(vinyl alcohol)/polyacrylamide (PVA/PAM) DN hydrogels were prepared by in situ polymerization, which were then treated with Hofmeister series ions (Cit3-, SO42-, and Cl-) to achieve H-PVA/PAM DN hydrogels. Among the three Hofmeister ions, the DN hydrogel treated with Cit3- (named PVA/PAM-Cit) showed the densest microstructure and the highest crystallinity degree. In this context, PVA/PAM-Cit exhibited a tensile strength of 18.9 ± 1.6 MPa, a compressive strength of 102.3 ± 7.9 MPa, a tensile modulus of 10.6 ± 2.1 MPa, a compressive modulus of 8.9 ± 0.8 MPa, and a roughness of 66.2 ± 4.2 MJ m-3, respectively, which were the highest strength and modulus, and the second highest toughness when compared with those of the reported PVA and PVA based DN hydrogels so far. It also showed an extreme high elasticity, which could maintain a stress of 99.2% after 500 cycles of fatigue testing. Additionally, PVA/PAM-Cit can promote the adhesion, spreading and proliferation of chondrocytes. These results verify that such a strong, tough, and elastic hydrogel could be a novel candidate material for articular cartilage replacement.

Tough and elastic hydrogels based on robust hydrophobicity-assisted metal ion coordination for flexible wearable devices.

Flexible wearable sensors that combine excellent flexibility, high elasticity, sensing capabilities, and outstanding biocompatibility are gaining increasing attention. In this study, we successfully develop a robust and elastic hydrogel-based flexible wearable sensor by modulating molecular structures combined with metal ion coordination. We leverage three N-acryloyl amino acid monomers, including N-acryloyl glycine (AG), N-acryloyl alanine (AA), and N-acryloyl valine (AV) with different hydrophobic groups adjacent to the carboxyl group, to copolymerize with acrylamide (AM) in the presence of Zr4+ for hydrogel preparation in one step (P(AM3-AG/AA/AV0.06)-Zr0.034+ hydrogels). Our investigation reveals that the P(AM3-AV0.06)-Zr0.034+ hydrogel with the most hydrophobic side group demonstrates superior mechanical properties (1.1 MPa tensile stress, 3566 kJ m-3 toughness and 1.3 kJ m-2 fracture energy) and resilience to multiple tensile (30% strain, 500 cycles) and compression cycling (50% strain, 500 cycles). Moreover, the P(AM3-AV0.06)-Zr0.034+ hydrogel exhibits good biocompatibility and high conductivity (1.1 S m-1) and responsivity (GF = 16.21), and is proved to be suitable as a flexible wearable sensor for comprehensive human activity monitoring.

A stiff and tough triple-shape memory hydrogel triggered at body temperature by hydrophobic association and electrostatic interaction

While triple-shape memory hydrogels (TSMHs) are considered promising materials for intelligent medical devices, obtaining TSMHs triggered at the human body temperature with adequate mechanical performance remains challenging. Herein, a stiff and tough TSMH with a wide glass transition temperature (Tg) range at approximately 36 °C is constructed by copolymerizing hydrophobic 2-aminoethyl methacrylate isopropyl carbamate (IMA) with zwitterionic sulfobetaine methacrylate (SBMA). While the introduction of SBMA into the poly(2-aminoethyl methacrylate isopropyl carbamate) (PIMA) polymer chain weakens the ultra-strong hydrophobic association, it causes an electrostatic interaction, which increases the flexibility of the copolymer chains and the cross-linking density of the network. Based on these structural characteristics, the poly(2-aminoethyl methacrylate isopropyl carbamate-co- sulfobetaine methacrylate) [P(IMA-co-SBMA)] hydrogels show reasonable triple shape memory effect with wide Tg ranging from 22 °C to 46 °C, Young's modulus from 2.82 MPa to 22.15 MPa, and fracture strain from 43 % to 444 %. This study provides a novel strategy for balancing the mechanical properties and Tg of TSMHs as materials for intelligent medical devices.

Biomimicking natural wood to fabricate isotropically super-strong, tough, and transparent hydrogels for strain sensor and triboelectric nanogenerator applications

We describe an efficient wood-inspired biomimicking strategy integrating multiscale structures to synthesize isotropically strong, tough, conductive, and transparent hydrogels as strain sensors and self-powered triboelectric nanogenerators.

A tough, antibacterial and antioxidant hydrogel dressing accelerates wound healing and suppresses hypertrophic scar formation in infected wounds

Wound management is an important issue that places enormous pressure on the physical and mental health of patients, especially in cases of infection, where the increased inflammatory response could lead to severe hypertrophic scars (HSs). In this study, a hydrogel dressing was developed by combining the high strength and toughness, swelling resistance, antibacterial and antioxidant capabilities. The hydrogel matrix was composed of a double network of polyvinyl alcohol (PVA) and agarose with excellent mechanical properties. Hyperbranched polylysine (HBPL), a highly effective antibacterial cationic polymer, and tannic acid (TA), a strong antioxidant molecule, were added to the hydrogel as functional components. Examination of antibacterial and antioxidant properties of the hydrogel confirmed the full play of the efficacy of HBPL and TA. In the in vivo studies of methicillin-resistant Staphylococcus aureus (MRSA) infection, the hydrogel had shown obvious promotion of wound healing, and more profoundly, significant suppression of scar formation. Due to the common raw materials and simple preparation methods, this hydrogel can be mass produced and used for accelerating wound healing while preventing HSs in infected wounds.

Penetration enhancers strengthen tough hydrogel bioadhesion and modulate locoregional drug delivery.

The human body possesses natural barriers, such as skin and mucosa, which limit the effective delivery of therapeutics and integration of medical devices to target tissues. Various strategies have been deployed to breach these barriers mechanically, chemically, or electronically. The development of various penetration enhancers (PEs) offers a promising solution due to their ability to increase tissue permeability using readily available reagents. However, existing PE-mediated delivery methods often rely on weak gel or liquid drug formulations, which are not ideal for sustained local delivery. Hydrogel adhesives that can seamlessly interface biological tissues with controlled drug delivery could potentially resolve these issues. Here, we demonstrate that tough adhesion between drug-laden hydrogels and biological tissue (e.g. skin and tumours) can lead to effective local delivery of drugs deep into targeted tissues by leveraging the enhanced tissue penetration mediated by PEs. The drug release profile of the hydrogel adhesives can be fine-tuned by further engineering the nanocomposite hydrogel matrix to elute chemotherapeutics from 2 weeks to 2 months. Using a 3D tumour spheroid model, we demonstrated that PEs increased the cancer-killing effectiveness of doxorubicin by facilitating its delivery into tumour microtissues. Therefore, the proposed tough bioadhesion and drug delivery strategy modulated by PEs holds promise as a platform technique to develop next-generation wearable and implantable devices for cancer management and regenerative medicine.

Facile and fast preparation of stretchable, self-adhesive, moisturizing, antifreezing and conductive tough hydrogel for wearable strain sensors

Stretchable, self-adhesive, moisturizing, antifreezing and conductive tough hydrogels for wearable strain sensors were conveniently and quickly prepared based on the catalytic mechanism of metal ions.