Controlling Particle Morphologies at Fluid Interfaces: Macro- and Micro- approaches

Abstract

The controlled generation of varying shaped particles is important for many applications: consumer goods, biomedical diagnostics, food processing, adsorbents and pharmaceuticals which can benefit from the availability of geometrically complex and chemically inhomogeneous particles. This thesis presents two approaches to spherical and non-spherical particle synthesis using macro and microfluidics. In the first approach, a droplet microfluidic technique is explored to fabricate spherical conducting polymer, polyaniline, particles with precise control over morphology and functionality. Microfluidics has recently emerged as an important alternate to the synthesis of complex particles. The conducting polymer, polyaniline, is widely used and known for its stability, high conductivity, and favorable redox properties. In this approach, monodisperse micron-sized polyaniline spherical particles were synthesized using two-phase droplet microfluidics from Aniline and Ammonium persulfate oxidative polymerization in an oil-based continuous phase. The morphology of the polymerized particles is porous in nature which can be used for encapsulation as well as controlled release applications. Encapsulation of an enzyme, glucose oxidase, was also performed using the technique to synthesize microspheres for glucose sensing. The polymer microspheres were characterized using SEM, UV-Vis and EDX to understand the relationship between their microstructure and stability. In the second approach, molten drop impact in a cooling aqueous medium to generate non-spherical particles was explored. Viscoelastic wax based materials are widely used in many applications and their performance and application depends on the particle morphology and size. The deformation of millimeter size molten wax drops as they impacted an immiscible liquid interface was investigated. Spherical molten wax drops impinged on a cooling water bath, then deformed and as a result of solidification were arrested into various shapes such as ellipsoids, mushrooms, spherulites and discs. The final morphology of the wax particles is governed by the interfacial, inertial, viscous and thermal effects, which can be studied over a range of Weber, Capillary, Reynolds and Stefan numbers. A simplified Stefan problem for a spherical drop was solved. The time required to initiate a phase transition at the interface of the molten wax and water after impact was estimated and correlated with the drop deformation history and final wax particle shape to develop a capability to predict the shape. While the microfluidic synthesis approach offers precise control over morphology and functionality, large particle throughput is a limitation. The drop impact in a liquid medium emulsion approach is limited to crosslinking or heat sensitive materials but can be extended to large scale production for industrial applications. Both approaches are simple, robust and cost effective making them viable and attractive solutions for complex particle synthesis. The choice of the approach is dependent on considerations such as particle material, size, shape, throughput and end application.