Dimerization of sub-nanoscale molecular clusters affords broadly tuneable viscoelasticity above the glass transition temperature.

Materials with promising mechanical performance generally demonstrate requirements for the critical sizes of their key building units, entanglements and crystal grains. Herein, only with van der Waals interaction, viscoelasticity with broad tunability has been facilely achieved below the critical size limits: the dimers of ∼1 nm polyhedral oligomeric silsesquioxane (POSS) with < 4 kD and size < 5 nm, which demonstrate distinct material physics compared to that of polymer nanocomposites of POSS. The dimeric POSSs are confirmed by scattering and calorimetrical measurements to be intrinsic glassy materials with glass transition temperatures ( s) lower than room temperature.

A Transparent, Highly Stretchable, Solvent-Resistant, Recyclable Multifunctional Ionogel with Underwater Self-Healing and Adhesion for Reliable Strain Sensors.

Ionogels have gained increasing attentions as a flexible conductive material. However, it remains a big challenge to integrate multiple functions into one gel that can be widely applied in various complex scenes. Herein, a kind of multifunctional ionogels with a combination of desirable properties, including transparency, high stretchability, solvent and temperature resistance, recyclability, high conductivity, underwater self-healing ability, and underwater adhesiveness is reported.

Dynamic bonds enable high toughness and multifunctionality in gelatin/tannic acid-based hydrogels with tunable mechanical properties.

Biopolymer-based functional hydrogels with excellent mechanical properties are desired, but their fabrication remains a challenge. Learning from the tofu-making process, we developed a freely formable hydrogel with high toughness and stiffness from the hydrogen bond-rich coacervation of tannic acid and gelatin through a simple hot-pressing process that transforms the coacervate particles into a bulk hydrogel. The mechanical properties of the obtained gelatin/tannic acid hydrogel (G/T gel) can be controlled by tuning the weight ratio of tannic acid to gelatin in the gel.

Polymer Topology Reinforced Synergistic Interactions among Nanoscale Molecular Clusters for Impact Resistance with Facile Processability and Recoverability.

The intrinsic conflicts between mechanical performances and processability are main challenges to develop cost-effective impact-resistant materials from polymers and their composites. Herein, polyhedral oligomeric silsesquioxanes (POSSs) are integrated as side chains to the polymer backbones. The one-dimension (1D) rigid topology imposes strong space confinements to realize synergistic interactions among POSS units, reinforcing the correlations among polymer chains.

Effect of mesoscale phase contrast on fatigue-delaying behavior of self-healing hydrogels.

We investigate the fatigue resistance of chemically cross-linked polyampholyte hydrogels with a hierarchical structure due to phase separation and find that the details of the structure, as characterized by SAXS, control the mechanisms of crack propagation. When gels exhibit a strong phase contrast and a low cross-linking level, the stress singularity around the crack tip is gradually eliminated with increasing fatigue cycles and this suppresses crack growth, beneficial for high fatigue resistance. On the contrary, the stress concentration persists in weakly phase-separated gels, resulting in low fatigue resistance.

Unexpected Elasticity in Assemblies of Glassy Supra-Nanoparticle Clusters.

Granular materials, composed of densely packed particles, are known to possess unique mechanical properties that are highly dependent on the surface structure of the particles. A microscopic understanding of the structure-property relationship in these systems remains unclear. Here, supra-nanoparticle clusters (SNPCs) with precise structures are developed as model systems to elucidate the unexpected elastic behaviors.

Polyzwitterions as a Versatile Building Block of Tough Hydrogels: From Polyelectrolyte Complex Gels to Double-Network Gels.

The high water content of hydrogels makes them important as synthetic biomaterials, and tuning the mechanical properties of hydrogels to match those of natural tissues without changing chemistry is usually difficult. In this study, we have developed a series of hydrogels with varied stiffness, strength, and toughness based on a combination of poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS), a strong acidic polyelectrolyte, and poly--(carboxymethyl)-,-dimethyl-2-(methacryloyloxy) ethanaminium) (PCDME), a polyzwitterion with a weak acidic moiety. We demonstrate that modifying the true molar ratio, , of PCDME to PAMPS results in four unique categories of hydrogels with different swelling ratios and Young's moduli.

Fiber-Reinforced Viscoelastomers Show Extraordinary Crack Resistance That Exceeds Metals.

Soft fiber-reinforced polymers (FRPs), consisting of rubbery matrices and rigid fabrics, are widely utilized in industry because they possess high specific strength in tension while allowing flexural deformation under bending or twisting. Nevertheless, existing soft FRPs are relatively weak against crack propagation due to interfacial delamination, which substantially increases their risk of failure during use. In this work, a class of soft FRPs that possess high specific strength while simultaneously showing extraordinary crack resistance are developed.

Mesoscale bicontinuous networks in self-healing hydrogels delay fatigue fracture.

Load-bearing biological tissues, such as muscles, are highly fatigue-resistant, but how the exquisite hierarchical structures of biological tissues contribute to their excellent fatigue resistance is not well understood. In this work, we study antifatigue properties of soft materials with hierarchical structures using polyampholyte hydrogels (PA gels) as a simple model system. PA gels are tough and self-healing, consisting of reversible ionic bonds at the 1-nm scale, a cross-linked polymer network at the 10-nm scale, and bicontinuous hard/soft phase networks at the 100-nm scale.

Tough Bonding, On-Demand Debonding, and Facile Rebonding between Hydrogels and Diverse Metal Surfaces.

Hybrid systems of hydrogels and metals with tough bonding may find widespread applications. Here, a simple and universal method to obtain strong adhesion between hydrogels and diverse metal surfaces, such as titanium, steel, nickel, tantalum, argentum, and aluminum, with adhesion energy up to >1000 J m is reported. To achieve such, the metal surfaces are instantly modified with a linker molecule via soaking, dip-coating, or drop-casting.

Elastic-Plastic Transformation of Polyelectrolyte Complex Hydrogels from Chitosan and Sodium Hyaluronate.

Hydrogels formed by polyelectrolyte complexation (PEC) of oppositely charged biopolymers, free of any chemical additives, are promising biomaterials. In this work, the mechanical behavior of hydrogels consisting of positively charged chitosan and negatively charged sodium hyaluronate (HA) at balanced charge composition is investigated. These hydrogels exhibit strong tensile strain and strain rate dependence.

Multiscale Energy Dissipation Mechanism in Tough and Self-Healing Hydrogels.

Understanding the energy dissipation mechanism during deformation is essential for the design and application of tough soft materials. We show that, in a class of tough and self-healing polyampholyte hydrogels, a bicontinuous network structure, consisting of a hard network and a soft network, is formed, independently of the chemical details of the hydrogels. Multiscale internal rupture processes, in which the double-network effect plays an important role, are found to be responsible for the large energy dissipation of these hydrogels.

Tough Hydrogels with Fast, Strong, and Reversible Underwater Adhesion Based on a Multiscale Design.

Hydrogels have promising applications in diverse areas, especially wet environments including tissue engineering, wound dressing, biomedical devices, and underwater soft robotics. Despite strong demands in such applications and great progress in irreversible bonding of robust hydrogels to diverse synthetic and biological surfaces, tough hydrogels with fast, strong, and reversible underwater adhesion are still not available. Herein, a strategy to develop hydrogels demonstrating such characteristics by combining macroscale surface engineering and nanoscale dynamic bonds is proposed.

Creating Stiff, Tough, and Functional Hydrogel Composites with Low-Melting-Point Alloys.

Reinforcing hydrogels with a rigid scaffold is a promising method to greatly expand the mechanical and physical properties of hydrogels. One of the challenges of creating hydrogel composites is the significant stress that occurs due to swelling mismatch between the water-swollen hydrogel matrix and the rigid skeleton in aqueous media. This stress can cause physical deformation (wrinkling, buckling, or fracture), preventing the fabrication of robust composites.

Stretching-induced ion complexation in physical polyampholyte hydrogels.

Recently, we have developed a series of charge balanced polyampholyte (PA) physical hydrogels by random copolymerization in water, which show extraordinarily high toughness, self-healing ability and viscoelasticity. The excellent performance of PA hydrogels is ascribed to dynamic ionic bond formation through inter- and intra-chain interactions. The randomness results in ionic bonds of wide strength distribution, the strong bonds, which serve as permanent crosslinking, imparting the elasticity, while the weak bonds reversibly break and re-form, dissipating energy.

Tough Physical Double-Network Hydrogels Based on Amphiphilic Triblock Copolymers.

A series of physical double-network hydrogels is synthesized based on an amphiphilic triblock copolymer. The gel, which contains strong hydrophobic domains and sacrificial dynamic bonds of hydrogen bonds, is stiff and tough, and even stiffens in concentrated saline solution. Furthermore, due to its supramolecular structure, the gel features improved self-healing and self-recovery abilities.

Self-Adjustable Adhesion of Polyampholyte Hydrogels.

Developing nonspecific, fast, and strong adhesives that can glue hydrogels and biotissues substantially promotes the application of hydrogels as biomaterials. Inspired by the ubiquitous adhesiveness of bacteria, it is reported that neutral polyampholyte hydrogels, through their self-adjustable surface, can show rapid, strong, and reversible adhesion to charged hydrogels and biological tissues through the Coulombic interaction.

Molecular structure of self-healing polyampholyte hydrogels analyzed from tensile behaviors.

Recently, charge balanced polyampholytes (PA) have been found to form tough and self-healing hydrogels. This class of physical hydrogels have a very high equilibrated polymer concentration in water (ca. 40-50 wt%), and are strongly viscoelastic.

Free Reprocessability of Tough and Self-Healing Hydrogels Based on Polyion Complex.

Tough hydrogels with facile processability to reform into various shapes are required in many practical applications. In this work, we reported that a novel, tough, and self-healing physical hydrogel based on polyion complex (PIC) can be dissolved in 4 M NaCl solution to form a PIC solution. The PIC solution can be easily reprocessed into various shapes, such as thin films, sheets, fibers, and capsules, by using simple methods, such as casting and injection, while maintaining excellent mechanical properties comparable to, or even better than, the original hydrogel.

Oppositely charged polyelectrolytes form tough, self-healing, and rebuildable hydrogels.

A series of tough polyion complex hydrogels is synthesized by sequential homopolymerization of cationic and anionic monomers. Owing to the reversible interpolymer ionic bonding, the materials are self-healable under ambient conditions with the aid of saline solution. Furthermore, self-glued bulk hydrogels can be built from their microgels, which is promising for 3D/4D printing and the additive manufacturing of hydrogels.

A phase diagram of neutral polyampholyte - from solution to tough hydrogel.

Our recent study has revealed that neutral polyampholytes form tough physical hydrogels above a critical concentration C by forming ionic bonds of wide strength distribution. In this work, we systematically investigate the behavior of a polyampholyte system, poly(NaSS-co-DMAEA-Q), randomly copolymerized from oppositely charged monomers, sodium p-styrenesulfonate (NaSS) and acryloyloxethyltrimethylammonium chloride (DMAEA-Q) without and with a slight chemical cross-linking. A phase diagram of formulation has been constructed in the space of monomer concentration C and cross-linker density C.

Double network hydrogels from polyzwitterions: high mechanical strength and excellent anti-biofouling properties.

Polyzwitterionic materials, which have both cationic and anionic groups in the polymeric repeat unit, show excellent anti-biofouling properties and are drawing more attention in the biomedical field. In this study, we have successfully synthesized novel single network hydrogels and double network (DN) hydrogels from the zwitterionic monomer, N-(carboxymethyl)-N,N-dimethyl-2-(methacryloyloxy) ethanaminium, inner salt (CDME). The polyCDME (PCDME) single network hydrogel behaves like a hydrophilic neutral hydrogel and its properties are not sensitive to temperature, pH, or ionic strength over a wide range.

Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity.

Hydrogels attract great attention as biomaterials as a result of their soft and wet nature, similar to that of biological tissues. Recent inventions of several tough hydrogels show their potential as structural biomaterials, such as cartilage. Any given application, however, requires a combination of mechanical properties including stiffness, strength, toughness, damping, fatigue resistance and self-healing, along with biocompatibility.