The UK Government recently set targets for "net zero emissions" and "zero waste" as well as a 10 Point Plan for a Green Industrial Revolution. Even so, the UK currently sources, processes and deploys advanced materials based on unsustainable practices, including the use of fossil fuels and scarce, geologically hindered raw materials. This contributes to over 30% of the UK CO2 emissions, especially considering the import of raw precursors and materials. Our vision is to build our most important functional materials from bio-based resources which are locally available. These materials will lower CO2 emissions, helping the UK to reach the targeted zero emissions by 2050 while boosting high-performance, locally available technologies and creating new industries. They will form the cornerstone for a modern technology-dependent economy. This programme grant brings together the best UK academics and key industrial partners involved in the development of a new supply chain for sustainable materials and applications. We will accelerate novel pathways to manufacture advanced materials out of available UK bioresources while boosting their performance working with stakeholders in key industrial sectors (chemical industry, advanced materials, energy, waste, agriculture, forestry, etc). The combined food, forestry and agricultural waste in the UK amounts to approx.26.5m tonnes each year. There is no valuable economic chain in the UK to allow waste valorisation towards high value-added materials. Yet, by mass, functional materials provide the most viable route for waste utilisation, preferable over waste-to-energy. This Programme Grant will thus enhance the UK's capability in the critical area of affordable and sustainable advanced materials for a zero carbon UK economy, providing multidisciplinary training for the next generation of researchers, and support for a nascent next generation of an advanced materials industry

Our society is completely dependent upon polymers (plastics) in every facet of our lives; from clothes to computers to novel composites, cars and cosmetics. A key question is how can we continue to use and consume polymers in the future? In 2010 every citizen of the USA discarded 140 kg of plastic into land-fill and those figures are similar and rising in many other societies around the globe. As more economies move towards Western levels of consumption, we simply will not be able to continue to use polymers in the same way. There are alternative polymers that are derived from renewable resources, and learning to make and use these will have a significant positive impact and will help to alleviate the issues of landfill, particularly when the renewable polymers are degradable. But despite all the hype and expectation, renewable polymers currently account for less than 5% of all polymers produced commercially. This figure is growing but the problem is that most renewable polymers simply do not perform as well as the traditional commodity polymers that are derived from oil. In this proposal we focus upon utilising terpenes to form a range of valuable new polymers. Terpenes are derived from citrus waste ( eg. d-limonene from orange peel) and from wood waste (eg. the alpha- and beta-pinenes) and are already available on the multi-tonne scale and sold into markets from fragrances to aromas and healthcare. There have been significant efforts in the past to create polymers directly from terpenes because their structures contain alkene moieties that appear to offer the opportunity for polymerisation via free radical routes under simple, readily accessible conditions that could easily be scaled. Unfortunately, extensive studies have yielded only poor quality low molecular weight or cross-linked polymers that have not found commercial utility. Now, we will build on recent proof of concept studies at Nottingham that could overcome this log-jam. We have developed a simple and versatile approach to produce new terpene based monomers that can be easily "dropped-in" to existing commercial polymerisation processes. Our approach offers the possibility to use readily available free radical and controlled polymerisation routes to create new polymers and co-polymers that can be tailored for application across the commodity and specialty plastics landscape. To achieve these goals we have assembled a multidisciplinary academic team that brings together all of the key skills and expertise needed to deliver these new monomers and polymers, and to characterise their properties to determine suitable application areas. In addition, we will utilise strong input, support and advice from industry partners from across the polymer sector to target the new materials towards focussed potential applications and products.

Solid-state nuclear magnetic resonance (NMR) is a powerful technique for studying the molecular-level structure of complex and heterogeneous materials. However, even with the high magnetic fields available today, solid-state NMR suffers from low sensitivity, because of the small nuclear spin polarizations involved, so that long acquisitions or large samples are required. This problem is overwhelming for dilute species and limits the usefulness of NMR studies of e.g. surfaces, adsorbates or rare isotopes. Fortunately, weak NMR signals can be enhanced at low temperatures (~100 K) by dynamic nuclear polarisation (DNP) where the large electron spin polarisation from an implanted radical is transferred to nearby nuclei. Progress with high-power microwave sources has made DNP possible at the high fields found in modern NMR spectrometers (up to 21 T). Large signal enhancements up to 300-fold (at 9.4 T) have been achieved for frozen biomolecules, corresponding to a reduction by a factor of 100,000 in experiment time. DNP is therefore a transformative technology which will result in a significant increase in the sensitivity of solid-state NMR. The potential step-change in capability it offers will eventually allow the power of solid-state NMR to be brought to bear on many real-life materials for the first time. The information gained will inform progress in the design of new materials by research scientists and hence support the commercial development of new technologies by the industrial sector. However, despite the substantial signal gains obtained with DNP for the favourable cases described in the literature, reliability and reproducibility remain major issues, and in our experience some 50% of DNP-enhanced solid-state NMR studies of materials attempted at the Nottingham DNP MAS NMR Facility result in unworkably low enhancements (< ~5). One critical aspect of DNP is sample preparation (incorporation of the radical), with many factors currently requiring empirical optimization to maximize signal enhancement, and yet systematic studies are rarely carried out, mainly because DNP instrument time is limited. Surfaces, porous materials and nanoscale particulates are usually polarised after wetness impregnation of the free volume by a radical solution, and many factors (radical concentration, solvent volume, sample morphology etc.) require empirical optimization to maximize sensitivity. As a result, most DNP studies of materials rely on published protocols which often do not result in the expected signal enhancements. These issues of reliability and reproducibility within the context of sample preparation are a major obstacle to DNP ever achieving its full potential for the molecular-level characterization of materials. The proposed research aims to overcome these problems, in order to realise the potential impact of DNP, by developing new approaches to sample preparation. The research will make use of the state-of-the-art DNP-enhanced solid-state NMR instrumentation at the Nottingham DNP MAS NMR Facility (see Track Record) purchased with the aid of a £2.4M EPSRC Strategic Equipment grant. The main items of funding sought in this proposal comprise the access charges required to cover the use of the instrument and the salary costs for a postdoctoral researcher to carry out the programme. Success with these new approaches to sample preparation will make novel high-impact applications of DNP to materials possible. This aspect of the proposed research will inform progress in the design of new materials by our research collaborators from within Nottingham and support the commercial development of new technologies by our partners from the industrial sector.