Highly stretchable and tough hydrogels.

Hydrogels are used as scaffolds for tissue engineering, vehicles for drug delivery, actuators for optics and fluidics, and model extracellular matrices for biological studies. The scope of hydrogel applications, however, is often severely limited by their mechanical behaviour. Most hydrogels do not exhibit high stretchability; for example, an alginate hydrogel ruptures when stretched to about 1.2 times its original length. Some synthetic elastic hydrogels have achieved stretches in the range 10-20, but these values are markedly reduced in samples containing notches. Most hydrogels are brittle, with fracture energies of about 10 J m(-2) (ref. 8), as compared with ∼1,000 J m(-2) for cartilage and ∼10,000 J m(-2) for natural rubbers. Intense efforts are devoted to synthesizing hydrogels with improved mechanical properties; certain synthetic gels have reached fracture energies of 100-1,000 J m(-2) (refs 11, 14, 17). Here we report the synthesis of hydrogels from polymers forming ionically and covalently crosslinked networks. Although such gels contain ∼90% water, they can be stretched beyond 20 times their initial length, and have fracture energies of ∼9,000 J m(-2). Even for samples containing notches, a stretch of 17 is demonstrated. We attribute the gels' toughness to the synergy of two mechanisms: crack bridging by the network of covalent crosslinks, and hysteresis by unzipping the network of ionic crosslinks. Furthermore, the network of covalent crosslinks preserves the memory of the initial state, so that much of the large deformation is removed on unloading. The unzipped ionic crosslinks cause internal damage, which heals by re-zipping. These gels may serve as model systems to explore mechanisms of deformation and energy dissipation, and expand the scope of hydrogel applications.

Highly Stretchable and Tough Hydrogels below Water Freezing Temperature.

Hydrogels consist of hydrophilic polymer networks dispersed in water. Many applications of hydrogels rely on their unique combination of solid-like mechanical behavior and water-like transport properties. If the temperature is lowered below 0 °C, however, hydrogels freeze and become rigid, brittle, and non-conductive. Here, a general class of hydrogels that do not freeze at temperatures far below 0 °C, while retaining high stretchability and fracture toughness, is demonstrated. These hydrogels are synthesized by adding a suitable amount of an ionic compound to the hydrogel. The present study focuses on tough polyacrylamide-alginate double network hydrogels equilibrated with aqueous solutions of calcium chloride. The resulting hydrogels can be cooled to temperatures as low as -57 °C without freezing. In this temperature range, the hydrogels can still be stretched more than four times their initial length and have a fracture toughness of 5000 J m-2 . It is anticipated that this new class of hydrogels will prove useful in developing new applications operating under a broad range of environmental and atmospheric conditions.

Fire-Resistant Hydrogel-Fabric Laminates: A Simple Concept That May Save Lives.

There is a large demand for fabrics that can survive high-temperature fires for an extended period of time, and protect the skin from burn injuries. Even though fire-resistant polymer fabrics are commercially available, many of these fabrics are expensive, decompose rapidly, and/or become very hot when exposed to high temperatures. We have developed a new class of fire-retarding materials by laminating a hydrogel and a fabric. The hydrogel contains around 90% water, which has a large heat capacity and enthalpy of vaporization. When the laminate is exposed to fire, a large amount of energy is absorbed as water heats up and evaporates. The temperature of the hydrogel cannot exceed 100 °C until it is fully dehydrated. The fabric has a low thermal conductivity and maintains the temperature gradient between the hydrogel and the skin. The laminates are fabricated using a recently developed tough hydrogel to ensure integrity of the laminate during processing and use. A thermal model predicts the performance of the laminates and shows that they have excellent heat resistance in good agreement with experiments, making them viable candidates in life saving applications such as fire-resistant blankets or apparel.

Extremely Stretchable and Fast Self-Healing Hydrogels.

Dynamic crosslinking of extremely stretchable hydrogels with rapid self-healing ability is described. Using this new strategy, the obtained hydrogels are able to elongate 100 times compared to their initial length and to completely self-heal within 30 s without external energy input.

Laminar Tendon Composites with Enhanced Mechanical Properties.

PURPOSE: A strong isotropic material that is both biocompatible and biodegradable is desired for many biomedical applications, including rotator cuff repair, tendon and ligament repair, vascular grafting, among others. Recently, we developed a technique, called "bioskiving" to create novel 2D and 3D constructs from decellularized tendon, using a combination of mechanical sectioning, and layered stacking and rolling. The unidirectionally aligned collagen nanofibers (derived from sections of decellularized tendon) offer good mechanical properties to the constructs compared with those fabricated from reconstituted collagen. METHODS: In this paper, we studied the effect that several variables have on the mechanical properties of structures fabricated from tendon slices, including crosslinking density and the orientation in which the fibers are stacked. RESULTS: We observed that following stacking and crosslinking, the strength of the constructs is significantly improved, with crosslinked sections having an ultimate tens ile strength over 20 times greater than non-crosslinked samples, and a modulus nearly 50 times higher. The mechanism of the mechanical failure mode of the tendon constructs with or without crosslinking was also investigated. CONCLUSIONS: The strength and fiber organization, combined with the ability to introduce transversely isotropic mechanical properties makes the laminar tendon composites a biocompatiable material that may find future use in a number of biomedical and tissue engineering applications.

Hybrid Hydrogels with Extremely High Stiffness and Toughness.

The development of hydrogels for cartilage replacement and soft robotics has highlighted a challenge: load-bearing hydrogels need to be both stiff and tough. Several approaches have been reported to improve the toughness of hydrogels, but simultaneously achieving high stiffness and toughness remains difficult. Here we report that alginate-polyacrylamide hydrogels can simultaneously achieve high stiffness and toughness. We combine short- and long-chain alginates to reduce the viscosity of pregel solutions and synthesize homogeneous hydrogels of high ionic cross-link density. The resulting hydrogels can have elastic moduli of ∼1 MPa and fracture energies of ∼4 kJ m-2. Furthermore, this approach breaks the inverse relation between stiffness and toughness: while maintaining constant elastic moduli, these hydrogels can achieve fracture energies up to ∼16 kJ m-2. These stiff and tough hydrogels hold promise for further development as load-bearing materials.