Browsing by Author "Wanless, E"

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    Imaging the invisible: resolving polymer brush structure through a freeform bayesian analysis of neutron reflectometry data
    (Australian Institute of Nuclear Science and Engineering (AINSE), 2020-11-11) Gresham, IJ; Murdoch, TJ; Johnson, EC; Grant, W; Wanless, E; Prescott, SW; Nelson, A
    Surfaces covered with densely tethered polymer chains possess desirable properties and are ubiquitous in natural and human-made systems. These properties stem from the diffuse structure of these polymer brush interfaces; consequently, resolving their structure is key to better understanding and designing polymer brush systems. We have been using the PLATYPUS neutron reflectometer at the ACNS to achieve this structural resolution over the past six years, contributing to our understanding of brush structure, as well as fundamental polymer physics. However, the analysis of collected reflectometry data is not without significant challenges; Inflexible models preclude viable structures and the uncertainty around accepted profiles (known as spread) is challenging to quantify. Furthermore, there is no guarantee of profile uniqueness in reflectivity analysis - multiple structures may match the data equally well. Quantifying profile uniqueness and determining the structures that agree with collected data (known as multimodality) has not been previously attempted on brush systems. Historically, data analyses have used least-squares approaches, which do not satisfactorily determine profile spread and bypass the possibility of c. Here we will briefly document our journey in modelling neutron reflectometry data collected from polymer brush systems, culminating in the presentation of our developed methodology. In this methodology, we model our brush with a freeform profile that minimises assumptions regarding polymer conformation while only producing physically reasonable structures. This model is built within refnx‘s Bayesian statistical framework, which enables the characterisation of structural uncertainty and multimodality through Markov Chain Monte Carlo sampling. We demonstrate the rigour of our approach via a round-trip analysis of a simulated system before applying it to real data, examining the well-characterised collapse of a thermoresponsive brush. The method we describe is directly applicable to reflectometry experiments on soft and diffuse systems, but may also be generalised to other instruments where the “inverse problem” hampers data analysis.
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    A multilayered approach to polyfluorene water-based organic photovoltaics
    (Elsevier Science BV, 2012-07-01) Stapleton, A; Vaughan, B; Xue, BF; Sesa, E; Burke, K; Zhou, XJ; Bryant, G; Werzer, O; Nelson, A; Kilcoyne, ALD; Thomsen, L; Wanless, E; Belcher, W; Dastoor, P
    Water-based polymer nanoparticle dispersions offer the prospect of addressing two of the main challenges associated with printing large area organic photovoltaic (OPV) devices; namely how to control the nanoscale architecture of the active layer and eliminate the need for hazardous organic solvents during device fabrication. However, to date, the efficiencies of nanoparticulate-based devices have been inferior to that of the corresponding bulk-heterojunction devices. Here we present an approach for producing optimised OPV devices from polymer nanoparticles via the fabrication of multilayered device architectures. We show that by controlling both nanoparticle morphology and inter-particle interactions it is now possible to build polyfluorene OPV devices from aqueous dispersions of nanoparticles that are more efficient than the corresponding bulk heterojunction devices. In particular we show that: (1) the polyfluorene nanoparticle morphology is suited to effective charge separation, (2) thermal treatment of the deposited layers results in improved interparticle connectivity and effective charge transport, and (3) the optimal device thickness is a delicate balance between the repair of layer defects and the creation of stress cracking in the nanoparticulate film. As such, this work offers insights for the development of printable photovoltaic devices based on water-dispersed nanoparticulate formulations. © 2012, Elsevier Ltd.
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    The specific ion response of polyelectrolyte brushes depends on polymer and anion hydrophilicity
    (Australian Institute of Nuclear Science and Engineering, 2016-11-29) Murdoch, TJ; Willott, JD; de Vos, WM; Nelson, A; Prescott, SW; Wanless, E; Webber, JB
    We have previously shown that the pH and ionic strength response of weak, polybasic brushes is dependent on the location of the counterion within the Hofmeister series and the relative hydrophobicity of the polymer.[1-3] Recent measurements of a hydrophobic poly(2-diisopropylamino) ethyl methacrylate (PDPA) brush on Platypus reflectometer show that a collapsed conformation independent of anion identity is formed at low ionic strength, 0.1 mM. At higher ionic strengths, up to 500 mM, extended conformations are observed in potassium acetate solutions, while potassium thiocyanate solutions collapse the brush. Numerical self consistent field (nSCF) calculations allowed previous hypotheses regarding the accumulation and hydration strength of the counterions to be tested. Addition of a single Flory-Huggins interaction parameter (χ) analogous to the anion hydrophilicity was sufficient to replicate the measured brush behaviour.