Nanoscale Porosity in Microellipsoids Cloaks Interparticle Capillary Attraction at Fluid Interfaces.

Anisotropic particles pinned at fluid interfaces tend toward disordered multiparticle configurations due to large, orientationally dependent, capillary forces, which is a significant barrier to exploiting these particles to create functional self-assembled materials. Therefore, current interfacial assembly methods typically focus on isotropic spheres, which have minimal capillary attraction and no dependence on orientation in the plane of the interface. In order to create long-range ordered structures with complex configurations via interfacially trapped anisotropic particles, control over the interparticle interaction energy via external fields and/or particle engineering is necessary. Here, we synthesize colloidal ellipsoids with nanoscale porosity and show that their interparticle capillary attraction at a water-air interface is reduced by an order of magnitude compared to their smooth counterparts. This is accomplished by comparing the behavior of smooth, rough, and porous ellipsoids at a water-air interface. By monitoring the dynamics of two particles approaching one another, we show that the porous particles exhibit a much shorter-range capillary interaction potential, with scaling intriguingly different than theory describing the behavior of smooth ellipsoids. Further, interferometry measurements of the fluid deformation surrounding a single particle shows that the interface around porous ellipsoids does not possess the characteristic quadrupolar symmetry of smooth ellipsoids, and quantitatively confirms the decrease in capillary interaction energy. By engineering nanostructured surface features in this fashion, the interfacial capillary interactions between particles may be controlled, informing an approach for the self-assembly of complex two-dimensional microstructures composed of anisotropic particles.

Gradient stretching to produce variable aspect ratio colloidal ellipsoids.

Developing reliable synthetic methods for producing shape-anisotropic polymer colloids is essential for their use in novel functional materials. In designing such materials from ellipsoidal particles, it is often necessary to screen a wide range of particle sizes and aspect ratios to appropriately understand how microscopic particle characteristics dictate macroscopic material response. Here, we describe a technique to simultaneously produce a broad range of aspect ratio polymer ellipsoid samples from a single synthetic step. The technique extends the traditional film-stretching approach to create ellipsoids by introducing a gradient in strain and film cooling, which results in varying degrees of particle stretching. We empirically calibrate the device such that the final particle elongation may be predicted from the film characteristics, enabling the selective harvesting of ellipsoids with desired dimensions and which can be isolated by aspect ratio. The method is applied successfully to a wide range of seed particle diameters (500 nm - 10 µm) and enables the rapid synthesis of variable aspect ratio particles for systematic studies of anisotropic particles.