Philip G. Whitten

Progress toward robust polymer hydrogels

In this review we highlight new developments in tough hydrogel materials in terms of their enhanced mechanical performance and their corresponding toughening mechanisms. These mechanically robust hydrogels have been developed over the past 10 years with many now showing mechanical properties comparable with those of natural tissues. By first reviewing the brittleness of conventional synthetic hydrogels, we introduce each new class of tough hydrogel: homogeneous gels, slip-link gels, double-network gels, nanocomposite gels and gels formed using poly-functional crosslinkers. In each case we provide a description of the fracture process that may be occurring. With the exception of double network gels where the enhanced toughness is quite well understood, these descriptions remain to be confirmed. We also introduce material property charts for conventional and tough synthetic hydrogels to illustrate the wide range of mechanical and swelling properties exhibited by these materials and to highlight links between these properties and the network topology. Finally, we provide some suggestions for further work particularly with regard to some unanswered questions and possible avenues for further enhancement of gel toughness.

Artificial muscles based on polypyrrole/carbon nanotube laminates

A novel method for the periodical assembly of laminates of forest-drawn carbon nanotube (CNT) sheets and polypyrrole (PPy) is described. The method produces composite films in which the volume fraction and orientation of CNTs can be controlled. Actuator stroke and strength is increased and work capacity per cycle doubled when nanotube orientation is perpendicular to the actuation direction. Most importantly, these PPy/CNT laminates have dramatically decreased creep during actuation, which has been a major barrier for the application of PPy actuators.

Tough Supersoft Sponge Fibers with Tunable Stiffness from a DNA Self-Assembly Technique

Tough and soft: Highly porous, spongelike materials self-assemble by calcium ion condensation of DNA-wrapped carbon nanotubes (SWNTs-DNA; see picture, IL = ionic liquid). The toughness, modulus, and swellability of the electrically conductive sponges can be tuned by controlling the density and strength of interfiber junctions. The sponges have compliances similar to the softest natural tissue, while robust interfiber junctions give high toughness.

Direct sub-micrometer patterning of nanostructured conducting polymer films via a low-energy infrared laser

Despite the many attractive properties of conjugated polymers, their practical applications are often limited by the lack of a simple, scalable, and nondisruptive patterning method. Here, a direct, scalable, high-resolution patterning technique for conducting polymers is demonstrated that does not involve photoresists, masks, or postprocessing treatment. Complex, well-defined patterns down to sub-micrometer scales can be created from nanofibrous films of a wide variety of conducting polymers by photothermally welding the nanofibers using a low-energy infrared laser. The welding depth, structural robustness, and optical properties of the films are readily controlled. In addition, the electrical properties such as conductivity can be precisely tuned over a 7-order of magnitude range, while maintaining the characteristic tunable electronic properties in the nonwelded polyaniline regions.

The role of unbound oligomers in the nucleation and growth of electrodeposited polypyrrole and method for preparing high strength, high conductivity films.

Polypyrrole is a material with immensely useful properties suitable for a wide range of electrochemical applications, but its development has been hindered by cumbersome manufacturing processes. Here we show that a simple modification to the standard electrochemical polymerization method produces polypyrrole films of equivalently high conductivity and superior mechanical properties in one-tenth of the polymerization time. Preparing the film as a series of electrodeposited layers with thorough solvent washing between layering was found to produce excellent quality films even when layer deposition was accelerated by high current. The washing step between the sequentially polymerized layers altered the deposition mechanism, eliminating the typical dendritic growth and generating nonporous deposits. Solvent washing was shown to reduce the concentration of oligomeric species in the near-electrode region and hinder the three-dimensional growth mechanism that occurs by deposition of secondary particles from solution. As artificial muscles, the high density sequentially polymerized films produced the highest mechanical work output yet reported for polypyrrole actuators.

Crosslinking neat ultrathin films and nanofibres of pH-responsive poly(acrylic acid) by UV radiation

Electrospun polyelectrolyte hydrogel nanofibres are being developed for many applications including artificial muscles, scaffolds for tissue engineering, wound dressings and controlled drug release. For electrospun polyelectrolytes, a post-spinning crosslinking process is necessary for producing a hydrogel. Typically, radiation or thermal crosslinking routines are employed that require multifunctional crosslinking molecules and crosslink reaction initiators (free radical producers). Here, ultraviolet subtype-C (UVC) radiation was employed to crosslink neat poly(acrylic acid) (PAA) nanofibres and films to different crosslink densities. Specific crosslink initiators or crosslinking molecules are not necessary in this fast and simple process providing an advantage for biological applications. Scanning probe microscopy was used for the first time to measure the dry and wet dimensions of hydrogel nanofibres. The diameters of the swollen fibres decrease monotonically with increasing UVC radiation time. The fibres could be reversibly swollen/contracted by treatment with solutions of varying pH, demonstrating their potential as artificial muscles. The surprising success of UVC radiation exposure to achieve chemical crosslinks without a specific initiator molecule exploits the ultrathin dimensions of the PAA samples and will not work with relatively thick samples.

Liquid Crystalline Behavior of Graphene Oxide in the Formation and Deformation of Tough Nanocomposite Hydrogels

In this paper, we report the formation and transformation of graphene oxide (GO) liquid crystalline (LC) structures in the synthesis and deformation of tough GO nanocomposite hydrogels. GO aqueous dispersions form a nematic LC phase, while the addition of poly(N-vinylpyrrolidone) (PVP) and acrylamide (AAm), which are capable of forming hydrogen bonding with GO nanosheets, shifts the isotropic/nematic transition to a lower volume fraction of GO and enhances the formation of nematic droplets. During the gelation process, a phase separation of the polymers and GO nanosheets is accompanied by the directional assembly of GO nanosheets, forming large LC tactoids with a radial GO configuration. The shape of the large tactoids evolves from a sphere to a toroid as the tactoids increase in size. Interestingly, during cyclic uniaxial tensile deformation a reversible LC transition is observed in the very tough hydrogels. The isolated birefringent domains and the LC domains in the tactoids in the gels are highly oriented under a high tensile strain.

Evaluation of encapsulating coatings on the performance of polypyrrole actuators

Conjugated polymer actuators are electroactive materials capable of generating force and movement in response to an applied external voltage. Many potential biomedical and industrial applications require these actuators to operate in a liquid environment. However, immersion of uncoated conducting polymer actuators in non-electrolyte liquids greatly reduces their operating lifetime. Here, we demonstrate the use of spray coating as an effective and simple method to encapsulate polypyrrole (PPy) tri-layer bending actuators. Poly(styrene-b-isobutylene-b-styrene) (SIBS) was used as an encapsulating, compliant spray coating on PPy actuators. A significant enhancement in actuator lifetime in both air and water was observed by encapsulating the actuators. The change in stiffness and reduction in bending amplitude for coatings of different thickness was studied. A simple beam mechanics model describes the experimental results and highlights the importance of coating compliance for actuator coatings. The model may be used to evaluate other possible encapsulating materials.

Actuating individual electrospun hydrogel nanofibres

The actuation of a single hydrogel nanofibre is measured for the first time by AFM. The actuation stress generated was comparable to that produced by skeletal muscle and the actuation rate was significantly increased by the nanoscale dimensions of the fibre.

Ionic Liquid Solvated Polymer Networks for Stretchable Electronics

Electronic skin and textiles are two current applications of stretchable electronics that require compliant solid electrolytes. Ionic liquid solvated polymer networks that are both tough and elastic to high strains are ideal electrolytes for stretchable electronics. Robust ionogels eshibiting elasticity as large as 480% strain, breaking strength as high as 3.2 MPa and tear energy as high as 2.8 kJ m−2 were produced. These ionogels are within their glass-to-rubber transition at 20°C and are categorized as plasticisized polymer networks. At 20°C and 105 Hz the ionogels are a polymer glass that inhibits ionic conductivity. GRAPHICAL ABSTRACT