Microgels are colloidally stable, hydrogel microparticles that have previously been used in a range of (soft) material applications due to their tunable mechanical and chemical properties. Most commonly, thermo and pH-responsive poly(N-isopropylacrylamide) (pNIPAm) microgels can be fabricated by precipitation polymerization in the presence of the co-monomer acrylic acid (AAc). Traditionally pNIPAm microgels are synthesized in the presence of a crosslinking agent, such as N,N'-methylenebisacrylamide (BIS), however, microgels can also be synthesized under 'crosslinker free' conditions. The resulting particles have extremely low (<0.5%), core-localized crosslinking resulting from rare chain transfer reactions. AFM nanoindentation of these ultralow crosslinked (ULC) particles indicate that they are soft relative to crosslinked microgels, with a Young's modulus of ∼10 kPa. Furthermore, ULC microgels are highly deformable as indicated by a high degree of spreading on glass surfaces and the ability to translocate through nanopores significantly smaller than the hydrodynamic diameter of the particles. The size and charge of ULCs can be easily modulated by altering reaction conditions, such as temperature, monomer, surfactant and initiator concentrations, and through the addition of co-monomers. Microgels based on the widely utilized, biocompatible polymer polyethylene glycol (PEG) can also be synthesized under crosslinker free conditions. Due to their softness and deformability, ULC microgels are a unique base material for a wide variety of biomedical applications including biomaterials for drug delivery and regenerative medicine.

A material’s mechanical properties greatly control cell behavior at the cell-substrate interface. In this work, we demonstrate that microgel multilayers have unique elastic and viscoelastic-like properties that can be modulated to produce morphological changes in fibroblasts cultured on the film. Protein adsorption is also examined and the data are contrasted with the number of cells adhered. The dynamic interaction of cell and substrate is only partially explained by conventional understanding of surface-receptor interactions and substrate elasticity. Viscoelasticity, a mechanical property not often considered, plays a significant role at cellular length and time scales for microgel films.

Microgel multi-layer films assembled from anionic particles and linear polycation were prepared on elastomeric substrates and their self-healing properties studied. Dried films were imaged in situ during mechanical deformation and were determined to undergo plastic deformation in response to linear strain, leading to film buckling upon strain relaxation. Hydration leads to rapid reorganization of the film building blocks, permitting recovery of the film to the undamaged state. Additionally, films were determined to heal in the presence of high relative humidity environments, suggesting that film swelling and hydration is a major factor in the restoration of film integrity, and that full immersion in solvent is not required for healing. Films prepared from microgels with lower levels of acid content and/or polycation length, factors strongly connected to the charge density and presumably the connectivity of the film, also display self-healing characteristics.

Multilayer coatings made from hydrogel microparticles (microgels) are conceptually very simple materials: thin films composed of microgel building blocks held together by polyelectrolyte "glue". However, the apparent simplicity of their fabrication and structure belies extremely complex properties, including those of "dynamic" coatings that display rapid self-healing behavior in the presence of solvent. This contribution covers our work with these materials and highlights some of the key findings regarding damage mechanisms, healing processes, film structure/composition, and how the variation of fabrication parameters can impact self-healing behavior.