Fabricating mesoscale polymer ribbons with tunable mechanical properties via evaporative deposition and dewetting.

Synthetic replication of the precise mesoscale control found in natural systems poses substantial experimental challenges due to the need for manipulation across multiple length scales (from nano- to millimeter). We address this challenge by using a 'flow coating' method to fabricate polymer ribbons with precisely tunable dimensions and mechanical properties. Overcoming barriers that previously limited the achievable range of properties with this method, we eliminate the need for substrate patterning and post-processing etching to facilitate the production of high aspect ratio, filament-like ribbons across a range of polymers-from glassy polystyrene to elastomeric poly(butadiene), as well as poly(butadiene-block-styrene). Our method uniquely enables the preservation of chemical fidelity, composition, and dimensions of these ribbons, leveraging polymers with elastic moduli from GPa to tens of MPa to achieve multi-scale features. We demonstrate the role of the elastocapillary length (γ/E) in determining morphological outcomes, revealing the increase in curvature with lower elastic modulus. This finding underscores the intricate relationship among surface tension, elastic modulus, and resultant structural form, enabling control over the morphology of mesoscale ribbons. The soft (MPa) polybutadiene-based ribbons exemplify our method's utility, offering structures with significant extensibility, resilience, and ease of handling, thus expanding the potential for future applications. This work advances our understanding of the fundamental principles governing mesoscale structure formation and unlocks new possibilities for designing soft materials with tailored properties, mirroring the complexity and functionality observed in nature.

One-Step Synthesis of Biphasic, Cavity-forming Polymer Particles via Dispersion Copolymerization of Styrene and Sulfobetaine Methacrylate.

A one-step dispersion copolymerization technique is demonstrated to fabricate biphasic particles as an approach to streamline the production of particles with complex morphology. The model system studies a monomer feed of hydrophobic styrene and hydrophilic, zwitterionic sulfobetaine methacrylate (SBMA) in a water/isopropanol cosolvent mixture. The resulting particles have a core-shell morphology that can be transformed, simply by washing the particles with water, into particles with a single surface opening connected to an interior cavity. Results indicate that particle morphology is dependent on the presence of nanoscopic SBMA-rich aggregates in the initial reaction mixture to act as nucleation sites, forming an SBMA-rich core encased in a styrene-rich shell. Systematic study of the morphology evolution reveals that the difference in monomer solubility profile can be exploited to control compositional drift of the particle composition during copolymerization yielding copolymer with sufficiently different composition to form phase-separated particle morphology. When SBMA is replaced with various ionic comonomers, the cavity-forming morphology is observed when reaction conditions result in low solubility of the comonomer in the cosolvent mixture. Based on these results, design guidelines are developed that may be applied to a variety of systems requiring complex and responsive particles made from chemically distinct comonomer pairings.