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The role of particle shape in evaporation-induced auto-stratification in polydisperse colloidal suspensions is explored with molecular dynamics simulations of mixtures of spheres and aspherical particles. A unified framework based on the competition between diffusion and diffusiophoresis is proposed to understand the effects of shape and size dispersity. In general, particles diffusing more slowly (e.g., larger particles) tend to accumulate more strongly at the evaporation front. However, larger particles have larger surface areas and therefore greater diffusiophoretic mobility. Hence, they are more likely to be driven away from the evaporation front via diffusiophoresis. For a rapidly dried bidisperse suspension containing small and large spheres, the competition leads to “small-on-top” stratification. Here, we employ a computational model in which the diffusion coefficient is inversely proportional to particle mass. For a mixture of spheres and aspherical particles with similar mass, the diffusion contrast is reduced, and the spheres are always enriched at the evaporation front as they have the smallest surface area for a given mass and, therefore, the lowest diffusiophoretic mobility. For a mixture of solid and hollow spheres that have the same outer radius and thus the same surface area, the diffusiophoretic contrast is suppressed, and the system is dominated by diffusion. Consequently, the solid spheres, which have a larger mass and diffuse more slowly, accumulate on top of the hollow spheres. Finally, for a mixture of thin disks and long rods that differ significantly in shape but have similar mass and surface area, both diffusion and diffusiophoresis contrasts are suppressed, and the mixture does not stratify.
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Generalized Access to Mesoporous Inorganic Particles and Hollow Spheres from Multicomponent Polymer Blends
Abstract Mesoporous inorganic particles and hollow spheres are of increasing interest for a broad range of applications, but synthesis approaches are typically material specific, complex, or lack control over desired structures. Here it is reported how combining mesoscale block copolymer (BCP) directed inorganic materials self‐assembly and macroscale spinodal decomposition can be employed in multicomponent BCP/hydrophilic inorganic precursor blends with homopolymers to prepare mesoporous inorganic particles with controlled meso‐ and macrostructures. The homogeneous multicomponent blend solution undergoes dual phase separation upon solvent evaporation. Microphase‐separated (BCP/inorganic precursor)‐domains are confined within the macrophase‐separated majority homopolymer matrix, being self‐organized toward particle shapes that minimize the total interfacial area/energy. The pore orientation and particle shape (solid spheres, oblate ellipsoids, hollow spheres) are tailored by changing the kind of homopolymer matrix and associated enthalpic interactions. Furthermore, the sizes of particle and hollow inner cavity are tailored by changing the relative amount of homopolymer matrix and the rates of solvent evaporation. Pyrolysis yields discrete mesoporous inorganic particles and hollow spheres. The present approach enables a high degree of control over pore structure, orientation, and size (15–44 nm), particle shape, particle size (0.6–3 µm), inner cavity size (120–700 nm), and chemical composition (e.g., aluminosilicates, carbon, and metal oxides).
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- Award ID(s):
- 1707836
- PAR ID:
- 10062560
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 30
- Issue:
- 27
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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