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The importance of the microstzructure of silicone hydrogels is widely appreciated but is poorly understood and minimally investigated. To ensure comfort and eye health, these materials must simultaneously exhibit both high oxygen and high water permeability. In contrast with most conventional hydrogels, the water content and water structuring within silicone hydrogels cannot be solely used to predict permeability. The materials achieve these opposing requirements based on a composite of nanoscale domains of oxygen‐permeable (silicone) and water‐permeable hydrophilic components. This study correlated characteristic ion permeation coefficients of a selection of commercially available silicone hydrogel contact lenses with their morphological structure and chemical composition. Differential scanning calorimetry measured the water structuring properties through subdivision of the freezing water component into polymer‐associated water (loosely bound to the polymer matrix) and ice‐like water (unimpeded with a melting point close to that of pure water). Small‐angle x‐ray scattering, and environmental scanning electron microscopy techniques were used to investigate the structural morphology of the materials over a range of length scales. Significant, and previously unrecognized, differences in morphology between individual materials at nanometer length scales were determined; this will aid the design and performance of the next generation of ocular biomaterials, capable of maintaining ocular homeostasis.

Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies.

Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform < THF < methanol) rather than the solubility order (where THF > chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies.

A series of novel block copolymers, processable from single organic solvents and subsequently rendered amphiphilic by thermolysis, have been synthesized using Grignard metathesis (GRIM) and reversible addition-fragmentation chain transfer (RAFT) polymerizations and azide-alkyne click chemistry. This chemistry is simple and allows the fabrication of well-defined block copolymers with controllable block lengths. The block copolymers, designed for use as interfacial adhesive layers in organic photovoltaics to enhance contact between the photoactive and hole transport layers, comprise printable poly(3-hexylthiophene)-block-poly(neopentyl p-styrenesulfonate), P3HT-b-PNSS. Subsequently, they are converted to P3HT-b-poly(p-styrenesulfonate), P3HT-b-PSS, following deposition and thermal treatment at 150 °C. Grazing incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS) revealed that thin films of the amphiphilic block copolymers comprise lamellar nanodomains of P3HT crystallites that can be pushed further apart by increasing the PSS block lengths. The approach of using a thermally modifiable block allows deposition of this copolymer from a single organic solvent and subsequent conversion to an amphiphilic layer by nonchemical means, particularly attractive to large scale roll-to-roll industrial printing processes.

Amphiphilic block copolymers within a range of volume fraction spontaneously form vesicles in aqueous solution, where a water core is enclosed by a polymer bilayer. Thin-film rehydration is a method used to produce vesicles routinely; a thin film is immersed in water, the film swells, and vesicles are formed which bleb off from the film surface. We have studied the early stages of hydration for PEOPBO block copolymer thin films under controlled water vapor conditions to understand this formation mechanism and so enable more efficient ways to encapsulate molecules using this method. Neutron and X-ray measurements show that the initial film exhibits weakly ordered structure with isotropic parallel and vertical orientation; the films initially swell and maintain the same orientation. At a critical point the layer swells rapidly and makes highly ordered lamellae structure at the same time. The lamellae are almost exclusively oriented parallel to the substrate and swell with increasing water absorption.

A pH‐responsive ABA triblock copolymer, comprising poly(methyl methacrylate)‐block‐poly(2‐(diethylamino)ethyl methacrylate)‐block‐poly(methyl methacrylate) [PMMA‐b‐PDEA‐b‐PMMA], has been cast into thin films with a well‐defined microstructure. Small Angle X‐ray Scattering (SAXS) and Atomic Force Microscopy (AFM) studies confirm that this copolymer forms a hydrogel consisting of PMMA spheres embedded within a polybase PDEA matrix, with the PMMA domains acting as physical cross‐links. The hydrogel has a pH‐reversible coil‐globule transition at around pH 4.5. This responsive physical property was exploited by immersing a sample of copolymer hydrogel in an aqueous solution containing a cyclic pH‐oscillating reaction, whereby the pH was continuously oscillated above and below the transition pH so as to induce autonomous volume transitions. The changes in microscopic and macroscopic length scales correlate closely during (de)swelling cycles, with affine behaviour occurring over five orders of magnitude.