Person:

Illeperuma, Widusha

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.

Hydrogels that undergo a volume phase transition in response to an external stimulus are of great interest because of their possible use as actuator materials. The performance of an actuator material is normally characterized by its force–stroke curve, but little is known about the force–stroke behavior of hydrogels. We use the theory of the ideal elastomeric gel to predict the force–stroke curves of a temperature-sensitive hydrogel and introduce an experimental method for measuring the curve. The technique is applied to PNIPAm hydrogels with low cross-link densities. The maximum force generated by the hydrogel increases with increasing cross-link density, while the maximum stroke decreases. The force–stroke curves predicted by the theory of the ideal elastomeric gel are in very good agreement with the experimental curves.

Hydrogels are widely used in many commercial products including Jell-O, contact lenses, and superabsorbent diapers. In recent decades, hydrogels have been under intense development for biomedical applications, such as scaffolds in tissue engineering, carriers for drug delivery, and valves in microfluidic systems. But the scope is severely limited as conventional hydrogels are weak and brittle and are not very stretchable. This thesis investigates the approaches that enhance the mechanical properties of hydrogels and their structural applications. We discov¬ered a class of exceptionally stretchable and tough hydrogels made from poly-mers that form networks via ionic and covalent crosslinks. Although such a hydrogel contains ~90% water, it can be stretched beyond 20 times its initial length, and has a fracture energy of ~9000 J/m2. The combination of large stretchability, remarkable toughness, and recoverability of stiffness and toughness, along with easy synthesis makes this material much superior over existing hydrogels. Extreme stretchability and blunted crack tips of these hydrogels question the validity of traditional fracture testing methods. We re-examine a widely used pure shear test method to measure the fracture energy. With the experimental and simulation results, we conclude that the pure shear test method can be used to measure fracture energy of extremely stretchable materials.
Even though polyacrylamide-alginate hydrogels have an extremely high toughness, it has a relatively low stiffness and strength. We improved the stiffness and strength by embedding fibers. Most hydrogels are brittle, allowing the fibers to cut through the hydrogel when the composite is loaded. But tough hydrogel composites do not fail by the fibers cutting the hydrogel; instead, it undergoes large deforming by fibers sliding through the matrix. Hydrogels were not considered as materials for structural applications. But with enhanced mechanical properties, they have opened up novel applications. This thesis aims to investigate the broader applications, well beyond those investigated so far. We show fiber reinforced tough hydrogels can dissipate a significant amount of energy at a tunable level of stress, making them suitable for energy absorbing applications such as inner layer of helmets. We develop inexpensive fire-retarding materials using tough hydrogels that provide superior protection from burn injuries. We also study hydrogels as actuators that can be used in soft robotics. Hydrogels contain mostly water and they freeze when the temperature drops below 00C and lose its functions. We demonstrate a new class of hydrogels that do not freeze and hydrogels that partially freeze below water freezing temperature. Partially freezing hydrogels are ideal for cooling applications such as gel packs and non-freezing hydrogels are useful in all the structural applications at low temperatures. This thesis will enable the use of inexpensive hydrogels in a new class of non-traditional structural applications where the mechanical behavior of the hydrogel is of prime importance.

Using strong fibers to reinforce a hydrogel is highly desirable but difficult. Such a composite would combine the attributes of a solid that provides strength and a liquid that transports matter. Most hydrogels, however, are brittle, allowing the fibers to cut through the hydrogel when the composite is loaded. Here we circumvent this problem by using a recently developed tough hydrogel. We fabricate a composite using an alginate-polyacrylamide hydrogel reinforced with a random network of stainless steel fibers. Because the hydrogel is tough, the composite does not fail by the fibers cutting the hydrogel; instead, it fails by the fibers pulling out of the hydrogel against friction. Both stiffness and strength can be increased significantly by adding fibers to the hydrogel. Before failure the composite dissipates a significant amount of energy, at a tunable level of stress, attaining large deformation. Potential applications of tough hydrogel composites include energy-absorbing helmets, tendon repair surgery, and stretchable biometric sensors.