Overview
Sulfur is a by-product of the petrochemicals industry, removed from oil and gas during purification. This sulfur can be turned into polymers by reaction with stabilising co-monomers, and there is interest in a range of applications for these, but greater understanding of the structure and properties of these polymers are needed, which this PhD will investigate.
About this opportunity
The development of inverse vulcanised (IV) polymers sparked interest in applications in energy storage, recyclability/sustainability, metal capture, optical materials, and antimicrobial surfaces – as well as the valorisation of industrial sulfur waste produced on a vast scale as a by-product of petrochemicals.
Aims: This project will investigate open questions of current importance to the field: 1) Differentiate thermal/catalytic/photochemical synthetic routes w.r.t to structure and properties; 2) Benchmark the impact of repeated reformation cycles on properties/structure; 3) Determine the nature of the reaction mechanism and structures (J. Am. Chem. Soc. 2023, 145, 12386–12397).
Methodology: Wide review of current IV literature producing a database of key monomers, proposed structures, side products and impurities. Parallel synthetic and computational workflows: Polymer fragments will be simulated with prediction of spectra, thermal (Tg) and mechanical (stress-strain) properties. A library of synthetic samples will be produced and evaluated across comonomer structures, synthetic routes, aging and recycling conditions. Techniques including: FTIR, NMR, PXRD, DSC, Raman, GPC, tensile testing. Published benefits would provide an invaluable reference to the field as well as crucial insights from the enabled comparisons.
The project relies on integrated experimental and simulation workflows, combined with database and large-dataset handling, aligned with the ethos and cohort support of the CDT. Including options to incorporate automation design for property testing during extended aging, recycling, and heat cycle investigations, as well as high-throughput screening and characterisation of large sample sets. Regarding the key simulation aspect: Traditionally molecular dynamics simulation of polymers is reserved to specialists because the “black box” options are not of sufficient quality for publication. The Troisi group have developed a simple workflow to enable the rapid generation of publication-quality simulation also by non-expert. Demonstration/trialling of this model by a (supported) PhD student whose focus is experimental will enable further rollout across future CDT cohorts incorporating and wider projects – building future capacity. Sulfur polymers are suitable to showcase this potential, as they have been underexplored in terms of computation, but highlighted for their need for such investigation (Progress in Polymer Science, 52, 2024, 101818). This project would be amenable to inputs from co-beneficial undergraduate projects, synthetic or computational and on Digital Chemistry course or otherwise.
This project will be supervised by Dr Tom Hasell and Prof Alessandro Troisi from the Department of Chemistry at the University of Liverpool. The Hasell group has experience in the synthesis of sulfur polymers, and group experience/training in synthesis and characterisation will aid rapid development and smooth running of the project.
The current computational methodology that would enable a non-expert to produce high-quality simulations of polymer has been developed in Troisi’s group from 2023.
The student will build a library of potential structures/fragments (alternative crosslinkers and mechanistic interpretations). They will synthesise multiple polymer samples under different conditions/crosslinkers and measure the spectra as well as physical properties (Hasell group), while simulating these structures and automating spectral predictions for them (Troisi group). They will compare experimental to simulated spectra (automated) and build a database comparing physical properties with spectral matches/grouping.
This project is expected to start in October 2026 and is offered under the EPSRC Centre for Doctoral Training in Digital and Automated Materials Chemistry based in the Materials Innovation Factory at the University of Liverpool, the largest industry-academia colocation in UK physical science. The successful candidate will benefit from training in robotic, digital, chemical and physical thinking, which they will apply in their domain-specific research in materials design, discovery and processing. PhD training has been developed with 35 industrial partners and is designed to generate flexible, employable, enterprising researchers who can communicate across domains.