Understanding complex polymer brush behaviour through improved reflectometry analysis methods

Abstract

Polymer brushes are arrays of densely surface-tethered polymer chains, and are of interest for two reasons. Firstly, they possess interfacial characteristics, such as antifouling and lubrication, that are desirable in many applications. Secondly, they are model systems that can provide additional insight into polymer behaviour due to their unique geometry. Observing the interfacial structure of these brush layers is critically important for understanding both their properties and the mechanisms driving the polymer behaviour.

To date, neutron reflectometry (NR) is the only technique that can demonstrably resolve the nanoscale structure of polymer brushes. However, these diffuse interfaces produce subtle features in the reflectometry data that challenge interpretation, with typical analyses failing to quantify the derived structure's uncertainty. Furthermore, the experimental potential of this technique for the study of brushes is only just being realised. This Thesis advances NR as a tool for studying polymer brush systems by establishing a robust analysis methodology that overcomes previous hurdles and demonstrating novel experimental techniques. In both cases, poly(N-isopropylacrylamide) (PNIPAM) brushes are used as model systems.

First, the polymer system is characterised through the novel observation of surface-initiated ARGET ATRP using time-resolved NR, and a study of the dry brush as a function of humidity and temperature. Second, methodologies are developed that allow for robust determination of both solvated and confined brush structures. Lastly, NR is used to elucidate the behaviour of PNIPAM brushes in complex environments. A novel confinement apparatus is used to investigate the structure of a PNIPAM brush under mechanical confinement and contrast-variation provides unparalleled insight into PNIPAM–surfactant systems. In each case, complementary techniques are essential in guiding reflectometry experiments and fully understanding the polymer system.

This work develops and demonstrates techniques that enhance the study of diffuse interfaces with the NR technique. Moreover, the holistic structural examination of PNIPAM undertaken sheds new light on the phase behaviour of this ostensibly well-understood polymer and highlights its rich interaction with surfactants.