Porous polymeric microparticles foamed with supercritical CO₂as scattering white pigments

Nowadays, titanium dioxide (TiO₂) is the most commercially relevant white pigment. Nonetheless, it is widely criticized due to its energy-intensive extraction and costly disposal of harmful by-products. Furthermore, recent studies discuss its potential harm for the environment and the human health. Environment-friendly strategies for the replacement of TiO₂as a white pigment can be inspired from nature. Here whiteness often originates from broadband light scattering air cavities embedded in materials with refractive indices much lower than that of TiO₂. Such natural prototypes can be mimicked by introducing air-filled nano-scale cavities into commonly used polymers. Here, we demonstrate the foaming of initially transparent poly(methyl methacrylate) (PMMA) microspheres with non-toxic, inert, supercritical CO₂. The properties of the foamed, white polymeric pigments with light scattering nano-pores are evaluated as possible replacement for TiO₂pigments. For that, the inner foam structure of the particles was imaged by phase-contrast x-ray nano-computed tomography (nano-CT), the optical properties were evaluated via spectroscopic measurements, and the mechanical stability was examined by micro compression experiments. Adding a diffusion barrier surrounding the PMMA particles during foaming allows to extend the foaming process towards smaller particles. Finally, we present a basic white paint prototype as exemplary application.