Microgels are colloidal hydrogel particles that exhibit a pronounced softness, which arises from the swollen nature of the constituent polymer network. This softness leads to a substantial deformability of such particles at liquid interfaces, which, in turn translates into a complex phase behaviour that can exhibit a phase transition between a non-close packed and a close packed arrangement. Here, we explore how the degree of swellability and deformability - and therefore the softness of the particles - affects the phase behaviour of microgels at the air/water interface upon compression. We use precipitation polymerization to synthesize poly(N-isopropylacrylamide) microgels with similar hydrodynamic radii in the collapsed state and systematically vary the degree of swellability by changing the crosslinking density. We spread these microgels onto the air/water interface of a Langmuir trough and characterize their interfacial properties by surface pressure - area isotherms. Furthermore, we continuously transfer the interfacial microgel monolayer during compression onto a solid substrate, thus encoding the complete phase diagram of the microgels with increasing particle density as a function of the position on the solid substrate. We investigate the microgel arrangement by atomic force microscopy and scanning electron microscopy and use image analysis to extract quantitative information on the interparticle distance and degree of order. We find that the phase transition is very sensitive to the crosslinking density and occurs at much lower surface pressures for less deformable particles. The softest microgels do not undergo any phase transition. Instead, the system exhibits pronounced local conformation changes around point defects with local five- and sevenfold symmetries, indicating that the geometry of the assembled structure effectively controls the local pressure experienced by the microgels.

Polymer blends with synergetic performance play an integral part in modern society. The discovery of compatible polymer systems often relies on strong chemical interactions. By contrast, the role of entropy in polymers is often neglected. In this work, we show that entropy effect could control the phase structure and mechanical behaviors of polymer blends. For weakly interacting polymer pairs, the seemingly small mixing entropy favors the formation of nanoscale cocontinuous structures. The abundant nanointerfaces could initiate large plastic deformations by crazing or shear, thus, transforming brittle polymers (elongation < 9%) into superductile materials (elongation ∼ 146%). The resultant polymer blends display high transparency, strength (∼70 MPa), and toughness (∼60 MJ/m 3 ) beyond most engineering plastics. The principle of entropy-driven blends may also be applied in other polymer systems, offering a strategy to develop mechanically robust bulk polymeric materials for emerging applications such as biomedicine and electronics.

Bio-based and biodegradable polymer composites, most notably poly(l-lactic acid) (PLLA) and poly(3-hydroxybutyrate) (PHB), represent a promising solution to replace conventional petroleum-based plastics. However, the brittleness and low miscibility of PLLA and PHB remain two major obstacles to practical applications. In this work, first PLLA/PHB blends are reported by melt mixing with a rigid component, poly(methyl methacrylate) (PMMA). Driven by favorable entropy, PMMA forms an interfacial nanolayer, which transforms the morphology of resultant blends. The ternary blends show 55-fold increase in elongation, 50-fold in toughness, and metal-like malleability (≈180°bending and twisting), while retaining its high stiffness (3.4 GPa) and strength (≈50 MPa). The mechanical improvement arises from numerous craze fibrils and shear deformation of the matrix, induced by the incorporated PMMA. Furthermore, this generic strategy can be applied to design other mechanically robust biocomposites for advanced green devices.

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