Edwin P. Chan

A biodegradable and biocompatible gecko-inspired tissue adhesive

There is a significant medical need for tough biodegradable polymer adhesives that can adapt to or recover from various mechanical deformations while remaining strongly attached to the underlying tissue. We approached this problem by using a polymer poly(glycerol-co-sebacate acrylate) and modifying the surface to mimic the nanotopography of gecko feet, which allows attachment to vertical surfaces. Translation of existing gecko-inspired adhesives for medical applications is complex, as multiple parameters must be optimized, including: biocompatibility, biodegradation, strong adhesive tissue bonding, as well as compliance and conformability to tissue surfaces. Ideally these adhesives would also have the ability to deliver drugs or growth factors to promote healing. As a first demonstration, we have created a gecko-inspired tissue adhesive from a biocompatible and biodegradable elastomer combined with a thin tissue-reactive biocompatible surface coating. Tissue adhesion was optimized by varying dimensions of the nanoscale pillars, including the ratio of tip diameter to pitch and the ratio of tip diameter to base diameter. Coating these nanomolded pillars of biodegradable elastomers with a thin layer of oxidized dextran significantly increased the interfacial adhesion strength on porcine intestine tissue in vitro and in the rat abdominal subfascial in vivo environment. This gecko-inspired medical adhesive may have potential applications for sealing wounds and for replacement or augmentation of sutures or staples.

Correlations between Mechanical and Electrical Properties of Polythiophenes

The elastic moduli of polythiophenes, regioregular poly(3-hexylthiophene) (P3HT) and poly-(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT), are compared to their field effect mobility showing a proportional trend. The elastic moduli of the films are measured using a buckling-based metrology, and the mobility is determined from the electrical characteristics of bottom contact thin film transistors. Moreover, the crack onset strain of pBTTT films is shown to be less than 2.5%, whereas that of P3HT is greater than 150%. These results show that increased long-range order in polythiophene semiconductors, which is generally thought to be essential for improved charge mobility, can also stiffen and enbrittle the film. This work highlights the critical role of quantitative mechanical property measurements in guiding the development of flexible organic semiconductors.

Mechanochromic Photonic Gels

Polymer gels are remarkable materials with physical structures that can adapt significantly and quite rapidly with changes in the local environment, such as temperature, light intensity, electrochemistry, and mechanical force. An interesting phenomenon observed in certain polymer gel systems is mechanochromism - a change in color due to a mechanical deformation. Mechanochromic photonic gels are periodically structured gels engineered with a photonic stopband that can be tuned by mechanical forces to reflect specific colors. These materials have potential as mechanochromic sensors because both the mechanical and optical properties are highly tailorable via incorporation of diluents, solvents, nanoparticles, or polymers, or the application of stimuli such as temperature, pH, or electric or strain fields. Recent advances in photonic gels that display strain-dependent optical properties are discussed. In particular, this discussion focuses primarily on polymer-based photonic gels that are directly or indirectly fabricated via self-assembly, as these materials are promising soft material platforms for scalable mechanochromic sensors.

Molecular layer-by-layer assembled thin-film composite membranes for water desalination

Molecular layer-by-layer (mLbL) assembled thin-film composite membranes fabricated by alternating deposition of reactive monomers on porous supports exhibit both improved salt rejection and enhanced water flux compared to traditional reverse osmosis membranes prepared by interfacial polymerization. Additionally, the well-controlled structures achieved by mLbL deposition further lead to improved antifouling performance.

Block Copolymer Photonic Gel for Mechanochromic Sensing

Dr. E. P. Chan , Dr. C. M. Stafford Polymers DivisionNational Institute of Standards and Technology100 Bureau Drive, MS 8542, Gaithersburg, MD 20899, USA E-mail: edwin.chan@nist.gov; chris.stafford@nist.gov Dr. J. J. Walish , Prof. E. L. Thomas Department of Materials Science and EngineeringMassachusetts Institute of TechnologyRm 6-113, 77 Massachusetts Avenue, Cambridge, MA 02139, USA

Spherical indentation testing of poroelastic relaxations in thin hydrogel layers

In this work, we present the Poroelastic Relaxation Indentation (PRI) testing approach for quantifying the mechanical and transport properties of thin layers of poly(ethylene glycol) hydrogels with thicknesses on the order of 200 μm. Specifically, PRI characterizes poroelastic relaxation in hydrogels by indenting the material at fixed depth and measuring the contact area-dependent load relaxation process as a function of time. With the aid of a linear poroelastic theory developed for thin or geometrically confined swollen polymer networks, we demonstrate that PRI can quantify the water diffusion coefficient, shear modulus and average pore size of the hydrogel layer. This approach provides a simple methodology to quantify the material properties of thin swollen polymer networks relevant to transport phenomena.

Poroelastic relaxation indentation of thin layers of gels

We develop a method of poroelastic relaxation indentation (PRI) to characterize thin layers of gels. The solution to the time-dependent boundary-value problem is obtained in a remarkably simple form, so that the force-relaxation curve obtained by indenting a gel readily determines all the poroelastic constants of the gel—the shear modulus, Poisson’s ratio, and the effective diffusivity. The method is demonstrated with a layer of polydimethylsiloxane immersed in heptane.

Quantifying the Stress Relaxation Modulus of Polymer Thin Films via Thermal Wrinkling

The viscoelastic properties of polymer thin films can have a significant impact on the performance in many small-scale devices. In this work, we use a phenomenon based on a thermally induced instability, termed thermal wrinkling, to measure viscoelastic properties of polystyrene films as a function of geometric confinement via changes in film thickness. With application of the appropriate buckling mechanics model for incompressible and geometrically confined films, we estimate the stress-relaxation modulus of polystyrene films by measuring the time-evolved wrinkle wavelength at fixed annealing temperatures. Specifically, we use time-temperature superposition to shift the stress relaxation curves and generate a modulus master curve for polystyrene films investigated here. On the basis of this master curve, we are able to identify the rubbery plateau, terminal relaxation time, and viscous flow region as a function of annealing time and temperatures that are well-above its glass transition. Our measurement technique and analysis provide an alternative means to measure viscoelastic properties and relaxation behavior of geometrically confined polymer films.

Viscoelastic properties of confined polymer films measured via thermal wrinkling

We present a new wrinkling-based measurement technique for quantifying the viscoelastic properties of confined polymer thin films. This approach utilizes real-time laser-light scattering to observe the kinetics of thermally-induced surface wrinkling, which evolves isothermally as a function of annealing time. Specifically, wrinkling is induced by applying a thermal stress to a polystyrene film that is sandwiched between a silicon substrate and an aluminium thin film superstrate. By following the time evolution of the wrinkle wavelength and amplitude, we can infer the rubbery modulus and shear viscosity of the polystyrene film with the aid of a theoretical model.

Tailor-Made Polyamide Membranes for Water Desalination

Independent control of the extrinsic and intrinsic properties of the polyamide (PA) selective layer is essential for designing thin-film composite (TFC) membranes with performance characteristics required for water purification applications besides seawater desalination. Current commercial TFC membranes fabricated via the well-established interfacial polymerization (IP) approach yield materials that are far from ideal because their layer thickness, surface roughness, polymer chemistry, and network structure cannot be separately tailored. In this work, tailor-made PA-based desalination membranes based on molecular layer-by-layer (mLbL) assembly are presented. The mLbL technique enables the construction of an ultrathin and highly cross-linked PA selective layer in a precisely and independently controlled manner. The mLbL-assembled TFC membranes exhibit significant enhancements in performance compared to their IP-assembled counterparts. A maximum sodium chloride rejection of 98.2% is achieved along with over 2.5 times higher water flux than the IP-assembled counterpart. More importantly, this work demonstrates the broad applicability of mLbL in fabricating a variety of PA-based TFC membranes with nanoscale control of the selective layer thickness and roughness independent of the specific polyamide chemistry.