Jeong-Yun Sun

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.

Stretchable, Transparent, Ionic Conductors

Hydrogel Stretch A range of stretchable, conductive materials can be made either by making an electrical conductor more stretchable or by adding an electrical conductor to a stretchable material. Keplinger et al. (p. 984; see the Perspective by Rogers) have added to the possibilities of an alternative stretchable ionic conductor based on a hydrogel material used to make deformable devices that are fully transparent to light over the visible spectrum and that can withstand high voltages and high frequencies. Stretchable ionic gels are fabricated into transparent actuators and loudspeakers. [Also see Perspective by Rogers] Existing stretchable, transparent conductors are mostly electronic conductors. They limit the performance of interconnects, sensors, and actuators as components of stretchable electronics and soft machines. We describe a class of devices enabled by ionic conductors that are highly stretchable, fully transparent to light of all colors, and capable of operation at frequencies beyond 10 kilohertz and voltages above 10 kilovolts. We demonstrate a transparent actuator that can generate large strains and a transparent loudspeaker that produces sound over the entire audible range. The electromechanical transduction is achieved without electrochemical reaction. The ionic conductors have higher resistivity than many electronic conductors; however, when large stretchability and high transmittance are required, the ionic conductors have lower sheet resistance than all existing electronic conductors.

Strengthening Alginate/Polyacrylamide Hydrogels Using Various Multivalent Cations

We successfully synthesized a family of alginate/polyacrylamide hydrogels using various multivalent cations. These hydrogels exhibit exceptional mechanical properties. In particular, we discovered that the hydrogels cross-linked by trivalent cations are much stronger than those cross-linked by divalent cations. We demonstrate stretchability and toughness of the hydrogels by inflating a hydrogel sheet into a large balloon, and the elasticity by using a hydrogel block as a vibration isolator in a forced vibration test. The excellent mechanical properties of these hydrogels may open up applications for hydrogels.

Wrinkled hard skins on polymers created by focused ion beam

A stiff skin forms on surface areas of a flat polydimethylsiloxane (PDMS) upon exposure to focused ion beam (FIB) leading to ordered surface wrinkles. By controlling the FIB fluence and area of exposure of the PDMS, one can create a variety of patterns in the wavelengths in the micrometer to submicrometer range, from simple one-dimensional wrinkles to peculiar and complex hierarchical nested wrinkles. Examination of the chemical composition of the exposed PDMS reveals that the stiff skin resembles amorphous silica. Moreover, upon formation, the stiff skin tends to expand in the direction perpendicular to the direction of ion beam irradiation. The consequent mismatch strain between the stiff skin and the PDMS substrate buckles the skin, forming the wrinkle patterns. The induced strains in the stiff skin are estimated by measuring the surface length in the buckled state. Estimates of the thickness and stiffness of the stiffened surface layer are estimated by using the theory for buckled films on compliant substrates. The method provides an effective and inexpensive technique to create wrinkled hard skin patterns on surfaces of polymers for various applications.

Highly stretchable, transparent ionic touch panel

Soft and still responsive Transparent touch screens, from large-panel interactive information maps to advanced cell phones, have become a part of daily life. However, such devices all use hard materials. Kim et al. have developed a soft touch panel based on polyacrylamide hydrogels (cross-linked polymers swollen with water) that are highly transparent and contain trapped LiCl to enhance conductivity. The hydrogels are soft and can be stretched extensively while still maintaining touch sensitivity. Science, this issue p. 682 Stretchable touch panels are made from polyacrylamide hydrogels loaded with lithium chloride. Because human-computer interactions are increasingly important, touch panels may require stretchability and biocompatibility in order to allow integration with the human body. However, most touch panels have been developed based on stiff and brittle electrodes. We demonstrate an ionic touch panel based on a polyacrylamide hydrogel containing lithium chloride salts. The panel is soft and stretchable, so it can sustain a large deformation. The panel can freely transmit light information because the hydrogel is transparent, with 98% transmittance for visible light. A surface-capacitive touch system was adopted to sense a touched position. The panel can be operated under more than 1000% areal strain without sacrificing its functionalities. Epidermal touch panel use on skin was demonstrated by writing words, playing a piano, and playing games.

Performance and biocompatibility of extremely tough alginate/polyacrylamide hydrogels

Although hydrogels now see widespread use in a host of applications, low fracture toughness and brittleness have limited their more broad use. As a recently described interpenetrating network (IPN) of alginate and polyacrylamide demonstrated a fracture toughness of ≈ 9000 J/m(2), we sought to explore the biocompatibility and maintenance of mechanical properties of these hydrogels in cell culture and in vivo conditions. These hydrogels can sustain a compressive strain of over 90% with minimal loss of Youngs Modulus as well as minimal swelling for up to 50 days of soaking in culture conditions. Mouse mesenchymal stem cells exposed to the IPN gel-conditioned media maintain high viability, and although cells exposed to conditioned media demonstrate slight reductions in proliferation and metabolic activity (WST assay), these effects are abrogated in a dose-dependent manner. Implantation of these IPN hydrogels into subcutaneous tissue of rats for 8 weeks led to mild fibrotic encapsulation and minimal inflammatory response. These results suggest the further exploration of extremely tough alginate/PAAM IPN hydrogels as biomaterials.

Highly Elastic and Conductive Human‐Based Protein Hybrid Hydrogels

A highly elastic hybrid hydrogel of methacryloyl-substituted recombinant human tropoelastin (MeTro) and graphene oxide (GO) nanoparticles are developed. The synergistic effect of these two materials significantly enhances both ultimate strain (250%), reversible rotation (9700°), and the fracture energy (38.8 ± 0.8 J m(-2) ) in the hybrid network. Furthermore, improved electrical signal propagation and subsequent contraction of the muscles connected by hybrid hydrogels are observed in ex vivo tests.

A Strain-Insensitive Stretchable Electronic Conductor: PEDOT:PSS/Acrylamide Organogels.

UNLABELLED Organogel-based stretchable electronic conductors exhibit electrical conduction even under a large stretching deformation of 300% without electrochemical reactions at DC voltages. The resistance change with stretching is almost strain-insensitive up to 50% strain and it remains at each deformation up to 1000 fatigue cycle. The polymeric conductive paths of PEDOT PSS are well preserved during the mechanical deformation.

Rupture of a highly stretchable acrylic dielectric elastomer

Dielectric elastomer transducers are often subject to large tensile stretches and are susceptible to rupture. Here we carry out an experimental study of the rupture behavior of membranes of an acrylic dielectric elastomer. Pure-shear test specimens are used to measure force-displacement curves, using samples with and without pre-cracks. We find that introducing a pre-crack into a membrane drastically reduces the stretch at rupture. Furthermore, we measure the stretch at rupture and fracture energy using samples of different heights at various stretch-rates. The stretch at rupture is found to decrease with sample height, and the fracture energy is found to increase with stretch-rate.

Debonding and fracture of ceramic islands on polymer substrates

We perform in-situ uniaxial tensile tests on polyimide substrates with patterned ceramic islands. The islands fail by either channel cracking or debonding from the substrate, depending on island size and thickness. To understand why different failure modes occur, we have analyzed the fracture and debonding of stiff islands on deformable substrates. Using finite element simulations, we find that the maximum tensile strain in the islands increases with island size, but decreases with island thickness. The maximum energy release rate for island/substrate debonding, in contrast, increases with both island size and thickness. Assuming that the islands do not fracture if the maximum tensile strain in the islands is lower than a critical value and that no debonding occurs if the maximum energy release rate is smaller than the interfacial toughness, the critical substrate strains for island fracture and debonding can be calculated. If the islands are thick and small, the critical debonding strain is small, and th...