Elastic microphase separation produces robust bicontinuous materials.

Bicontinuous microstructures are essential to the function of diverse natural and synthetic systems. Their synthesis has been based on two approaches: arrested phase separation or self-assembly of block copolymers. The former is attractive for its chemical simplicity and the latter, for its thermodynamic robustness. Here we introduce elastic microphase separation (EMPS) as an alternative approach to make bicontinuous microstructures. Conceptually, EMPS balances the molecular-scale forces that drive demixing with large-scale elasticity to encode a thermodynamic length scale. This process features a continuous phase transition, reversible without hysteresis. Practically, EMPS is triggered by simply supersaturating an elastomeric matrix with a liquid, resulting in uniform bicontinuous materials with a well-defined microscopic length scale tuned by the matrix stiffness. The versatility of EMPS is further demonstrated by fabricating bicontinuous materials with superior mechanical properties and controlled anisotropy and microstructural gradients. Overall, EMPS presents a robust alternative for the bulk fabrication of homogeneous bicontinuous materials.

ATRP Enhances Structural Correlations In Polymerization-Induced Phase Separation.

Synthetic methods to control the structure of materials at sub-micron scales are typically based on the self-assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano- and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase-separated poly-methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.

Three-dimensional printing of photonic colloidal glasses into objects with isotropic structural color.

Structural color is frequently exploited by living organisms for biological functions and has also been translated into synthetic materials as a more durable and less hazardous alternative to conventional pigments. Additive manufacturing approaches were recently exploited for the fabrication of exquisite photonic objects, but the angle-dependence observed limits a broader application of structural color in synthetic systems. Here, we propose a manufacturing platform for the 3D printing of complex-shaped objects that display isotropic structural color generated from photonic colloidal glasses. Structurally colored objects are printed from aqueous colloidal inks containing monodisperse silica particles, carbon black, and a gel-forming copolymer. Rheology and Small-Angle-X-Ray-Scattering measurements are performed to identify the processing conditions leading to printed objects with tunable structural colors. Multimaterial printing is eventually used to create complex-shaped objects with multiple structural colors using silica and carbon as abundant and sustainable building blocks.

Putting the Squeeze on Phase Separation.

Phase separation is a ubiquitous process and finds applications in a variety of biological, organic, and inorganic systems. Nature has evolved the ability to control phase separation to both regulate cellular processes and make composite materials with outstanding mechanical and optical properties. Striking examples of the latter are the vibrant blue and green feathers of many bird species, which are thought to result from an exquisite control of the size and spatial correlations of their phase-separated microstructures. By contrast, it is much harder for material scientists to arrest and control phase separation in synthetic materials with such a high level of precision at these length scales. In this Perspective, we briefly review some established methods to control liquid-liquid phase separation processes and then highlight the emergence of a promising arrest method based on phase separation in an elastic polymer network. Finally, we discuss upcoming challenges and opportunities for fabricating microstructured materials via mechanically controlled phase separation.

Enhancing the Refractive Index of Polymers with a Plant-Based Pigment.

Polymers are essential components of many nanostructured materials. However, the refractive indices of common polymers fall in a relatively narrow range between 1.4 and 1.6. Here, it is demonstrated that loading commercially-available polymers with large concentrations of a plant-based pigment can effectively enhance their refractive index. For polystyrene (PS) loaded with 67 w/w% ß-carotene (BC), a peak value of 2.2 near the absorption edge at 531 nm is achieved, while maintaining values above 1.75 across longer wavelengths of the visible spectrum. Despite high pigment loadings, this blend maintains the thermoforming ability of PS, and BC remains molecularly dispersed. Similar results are demonstrated for the plant-derived polymer ethyl cellulose (EC). Since the refractive index enhancement is intimately connected to the introduction of strong absorption, it is best suited to applications where light travels short distances through the material, such as reflectors and nanophotonic systems. Enhanced reflectance from films is experimentally demonstrated, as large as sevenfold for EC at selected wavelengths. Theoretical calculations highlight that this simple strategy can significantly increase light scattering by nanoparticles and enhance the performance of Bragg reflectors.

Structural color from solid-state polymerization-induced phase separation.

Structural colors are produced by wavelength-dependent scattering of light from nanostructures. While living organisms often exploit phase separation to directly assemble structurally colored materials from macromolecules, synthetic structural colors are typically produced in a two-step process involving the sequential synthesis and assembly of building blocks. Phase separation is attractive for its simplicity, but applications are limited due to a lack of robust methods for its control. A central challenge is to arrest phase separation at the desired length scale. Here, we show that solid-state polymerization-induced phase separation can produce stable structures at optical length scales. In this process, a polymeric solid is swollen and softened with a second monomer. During its polymerization, the two polymers become immiscible and phase separate. As free monomer is depleted, the host matrix resolidifies and arrests coarsening. The resulting polymeric composites have a blue or white appearance. We compare these biomimetic nanostructures to those in structurally-colored feather barbs, and demonstrate the flexibility of this approach by producing structural color in filaments and large sheets.

When Black and White make Green: the Surprising Interplay of Structure and Pigments.

The natural world is teeming with color, which originates either from the wavelength-dependent absorp- tion of light by pigments or from scattering from nanoscale structures, or both. While the latter ' structural color ' has been a topic of intense study in recent years, the most vibrant colors in nature involve contributions from both structure and pigment. The study of structure-pigment interactions in biological systems is currently in its infancy and could inspire more technological applications, such as sustainable, toxin-free pigments and more efficient light harvesting.

Controlled formation of chitosan particles by a clock reaction.

Clock reactions allow precise control of chemical composition in the time domain. Such nonlinear chemical systems have recently been introduced to mimic the self-assembly pathways common in living organisms. Here, we demonstrate the use of a clock reaction to trigger the formation of polymeric nanoparticles. By adjusting the delay of a formaldehyde clock reaction, we controlled the precipitation of chitosan to form particles with sizes tunable in a wide range (from about 200 to 600 nm diameter). The chemical structure of chitosan was not significantly perturbed by the clock reagents.

Metasurfaces Leveraging Solar Energy for Icephobicity.

Inhibiting ice accumulation on surfaces is an energy-intensive task and is of significant importance in nature and technology where it has found applications in windshields, automobiles, aviation, renewable energy generation, and infrastructure. Existing methods rely on on-site electrical heat generation, chemicals, or mechanical removal, with drawbacks ranging from financial costs to disruptive technical interventions and environmental incompatibility. Here we focus on applications where surface transparency is desirable and propose metasurfaces with embedded plasmonically enhanced light absorption heating, using ultrathin hybrid metal-dielectric coatings, as a passive, viable approach for de-icing and anti-icing, in which the sole heat source is renewable solar energy. The balancing of transparency and absorption is achieved with rationally nanoengineered coatings consisting of gold nanoparticle inclusions in a dielectric (titanium dioxide), concentrating broadband absorbed solar energy into a small volume. This causes a > 10 °C temperature increase with respect to ambient at the air-solid interface, where ice is most likely to form, delaying freezing, reducing ice adhesion, when it occurs, to negligible levels (de-icing) and inhibiting frost formation (anti-icing). Our results illustrate an effective unexplored pathway toward environmentally compatible, solar-energy-driven icephobicity, enabled by respectively tailored plasmonic metasurfaces, with the ability to design the balance of transparency and light absorption.