The University of Bath is inviting applications for the following PhD project based in the Department of Chemistry under the supervision of Dr Maciek Kopeć https://researchportal.bath.ac.uk/en/persons/maciek-kopec
Post-polymerisation modification is an alternative approach of synthesising otherwise inaccessible polymers. This project will explore post-polymerisation chemistry of polyacrylonitrile (PAN), an important polymer traditionally used as precursor to carbon fibres and various carbon nanomaterials,1 towards the preparation of new sustainable polymers and materials for energy conversion/storage.
The unique carbonisation chemistry of PAN results from the reactivity of the nitrile (cyano) side groups which undergo facile cyclisation and crosslinking upon heating. However, even though nitrile is a ubiquitous functional group in organic chemistry, its utilisation in PAN for purposes other than carbonisation has been limited. Given both reactivity of the nitrile moieties as well as commercial availability of PAN and other nitrile-containing polymers, nitrile transformations are promising reactions as a more general, widely applicable post-polymerisation approach.
Thus, the aim of the project will be to synthesise new polymeric systems via post-polymerisation reactions of the nitrile group. By employing controlled radical polymerisation techniques, such as atom transfer radical polymerisation (ATRP) or reversible addition fragmentation transfer (RAFT) polymerisation, well-defined PAN and its copolymers (e.g. commercially important styrene-acrylonitrile, SAN) will be prepared and transformed into novel functional materials.
The project will look at two main processes:
1. Transformation of the CN groups into reversible crosslinks. Reversibly crosslinked materials, namely covalent adaptable networks (CANs) exhibit multiple exciting properties such as chain topology-induced processability or self-healing. Modification of the nitrile group into moieties able to form reversible covalent bonds will enable preparation of CANs from a number of nitrile-containing polymers, as confirmed by a very recent work on nitrile rubber(2).
2. Carbonisation of PAN with sulphur for Lithium-Sulphur (Li-S) batteries. PAN-sulphur composites (SPAN) are one of the materials investigated as cathodes for Li-S batteries(1). New PAN-based precursors and carbonisation processes aimed at maximising the sulphur content in a composite, which is a crucial parameter in order to make such batteries commercially viable, will be tested.
The project will involve polymer synthesis by controlled polymerisation techniques, extensive characterisation by gel permeation/size exclusion chromatography (GPC/SEC), 1H and 13C NMR, thermal analysis (DSC, TGA, DMA) as well as final application testing of the prepared materials.
Applicants should hold, or expect to receive, a First Class or high Upper Second Class UK Honours degree (or the equivalent qualification gained outside the UK) in Chemistry or Materials Science, and should have an interest in polymer science. A master’s level qualification would also be advantageous. Non-UK applicants must meet our English language entry requirement http://www.bath.ac.uk/study/pg/apply/english-language/index.html
Formal applications should be made via the University of Bath’s online application form: https://samis.bath.ac.uk/urd/sits.urd/run/siw_ipp_lgn.login?process=siw_ipp_app&code1=RDUCH-FP01&code2=0014
Please ensure that you quote the supervisor’s name and project title in the ‘Your research interests’ section.
More information about applying for a PhD at Bath may be found here: http://www.bath.ac.uk/guides/how-to-apply-for-doctoral-study/
Anticipated start date: 28 September 2020.