Soft Colloids from p(NIPAm-co-AAc): Packing Dynamics and Structure

Abstract

Traditionally, the experimental model of choice for studying the structure and dynamics of glasses or crystals are hard-sphere colloids. An analogy with molecular or atomic materials is often drawn, in which each colloidal particle represents an atom or a molecule. Making the individual particles deformable allows an even wider range of phenomena to be observed. In this thesis, I report the three-dimensional confocal microscopic study of the structure and dynamics of aqueous suspensions of fluorescently labeled poly(N-Isopropylacrylamide)-co-(Acrylic Acid), or p(NIPAm-co-AAc), microgel particles of hydrodynamic diameter 1.0 - 1.5 μm. Image analysis techniques and particle tracking algorithms are used to quantify the particle dynamics and the suspension structure. The phase behavior of the suspensions is dependent on a number of factors including pH, temperature, and concentration. By adjusting the pH, the interactions between the microgel particles can be tuned from purely repulsive near neutral pH, to weakly attractive at low pH. At low pH and low concentration, dynamic arrest results mainly from crystallization driven by the attraction between particles; crystal nucleation occurs homogeneously throughout the sample. The dynamics is nucleation limited where fast crystallization follows a delay time. At low pH and high concentration, relaxation of the suspension is constrained and it evolves only slightly to form disordered solid. At neutral pH, the dynamics are a function of the particle number concentration only; a high concentration leads to the formation of a disordered soft glassy solid. Additionally, the three-dimensional image stacks are studied to determine crystal structure by calculating pair correlation functions, g(r), bond order parameters, and structure factors, s(q). The results show that crystal structure is independent of concentration, charge, size, and stiffness of particles remaining FCC under all conditions. At low concentrations and low pH, the structures formed are polycrystalline solids. Moreover, the ability of the particles to compress enables the suspensions to maintain their crystal structure when subjected to external stress. The results help us better understand the relationship between dynamics and structure in soft colloidal suspensions, enhance our ability to use the colloids to model materials, and improve applications of the colloids in industrial products.