The plastic products that are so endemic to modern life are made up of long-chain molecules known as polymers. There are many reasons why plastics are so appealing; one of the most important is that the polymer molecules are easily melted and squeezed into shaped moulds in order to produce complex geometries; another reason is that molecules can be aligned during processing to improve material properties along the alignment direction (as is the case, for example, in packaging films, plastic bottles and polymer fibres). In order to make better use of existing materials and to design new polymers for specific applications, engineers need the ability to predict the process conditions that will give particular polymer molecules a predetermined set of material properties within a product. In the past few decades, significant progress has been made in understanding and predicting how polymer molecules of different shapes and lengths respond to flow. Much of this progress has been made possible by studying model polymers, where all molecules are identical in shape and length, or monodisperse. In previous studies, we were able to show that, in these model systems, it is possible to predict a range of solid-state properties of products with molecular orientation, by making use of the rheological, or flow, properties. The main difference between commercial plastics and these model monodisperse polymers is that commercial plastics are made up of a distribution of polymer molecules of different lengths, known as polydisperse. Thus, in order to apply predictive models to commercial plastics, an understanding of how polymer chains of different lengths interact with each other is necessary. This study is aimed at developing models able to predict the mechanical and optical properties of processed polydisperse polymers, applicable to commercial plastics. In order to achieve this, the study will first focus on a special class of polymers known as bimodal blends, which are made up of a mixture of two different monodisperse polymers. By understanding how the different length scales of polymers in bimodal blends interact with one another when they are oriented, it will be possible to make progress in understanding the interactions between the multitude of length scales present in polydisperse commercial plastics. The research will involve an experimental study of the mechanical and optical properties of both bimodal blends and polydisperse commercial polymers that have been subjected to molecular orientation typical of commercial processes. Additionally, a neutron beam will be used to probe orientation in special blends in which one of the length scales is rendered invisible to the beam. The experiments will be used to inform and validate a set of models that can account for the interaction of polymer molecules of different lengths when predicting the solid-state properties that result after a given orientation process. The UK processes 4.8m tonnes of plastics each year, and the UK plastics industry contributed 2.1% of GDP in 2010. Because of comparatively high labour costs in the UK, the industry is focused on niche markets with highly optimised operations, and innovative companies operating at the cutting edge of technology. The research intends to empower the polymer industry to optimise resin composition to processes and products, and to enable solid-state property predictions of processed commercial polymers hitherto not possible. In the long term, this will drive the development of new polymers and new applications of polymers, help to shorten product development times, lead to existing polymers and processes better suited to their application, and help the UK polymer industry to remain a worldwide leader in the field.

Catalysis is a core area of science that lies at the heart of the chemicals industry - an immensely successful and important part of the overall UK economy, where in recent years the UK output has totalled over £50B annually and is ranked 7th in the world. This position is being maintained in the face of immense competition worldwide. For the UK to sustain its leading position it is essential that innovation in research is maintained, to achieve which the UK Catalysis Hub was established in 2013; and has succeeded over the last four years in bringing together over 40 university groups for innovative and collaborative research programmes in this key area of contemporary science. The success of the Hub can be attributed to its inclusive and open ethos which has resulted in many groups joining its network since its foundation in 2013; to its strong emphasis on collaboration; and to its physical hub on the Harwell campus in close proximity to the Diamond synchrotron, ISIS neutron source and Central Laser Facility, whose successful exploitation for catalytic science has been a major feature of the recent science of the Hub. The next phase of the Catalysis Hub will build on this success and while retaining the key features and structure of the current hub will extend its programmes both nationally and internationally. The core activities to which the present proposal relates include our coordinating activities, comprising our influential and well attended conference, workshop and training programmes, our growing outreach and dissemination work as well as the core management functions. The core catalysis laboratory facilities within the research complex will also be maintained and developed and two key generic scientific and technical developments will be undertaken concerning first sample environment and high throughput capabilities especially relating to facilities experimentation; and secondly to data management and analysis. The core programme will coordinate the scientific themes of the Hub, which in the initial stages of the next phase will comprise: - Optimising, predicting and designing new catalysts - Water - energy nexus - Catalysis for the Circular Economy and Sustainable Manufacturing - Biocatalysis and biotransformations The Hub structure is intrinsically multidisciplinary including extensive input from engineering as well as science disciplines and with strong interaction and cross-fertilisation between the different themes. The thematic structure will allow the Hub to cover the major areas of current catalytic science

Methoxycarbonylation is a process that converts cheap, widely available feedstocks (alkenes, carbon monoxide and methanol) into commercially-important intermediates for the chemicals industry. This process uses Pd-based catalysts and the best example is the reaction of the simplest alkene, ethene, to give the intermediate methyl methacrylate, which is used in the synthesis of plastics. More recently, alkenes such as vinyl acetate have been shown to undergo methoxycarbonylation to generate intermediates that are themselves useful as green solvents (low-volatility/biodegradable) or as monomers for the formation of biodegradable polymers. These have the potential to replace traditional materials such as polystyrene or polythene. Methoxycarbonylation of butadiene promises a new route to adipic acid, one of the co-monomers involved in the manufacture of nylon. As yet the methoxycarbonylation of vinyl acetate and butadiene have not been optimised and greater insight into these reactions is required before effective industrial processes are in place.A key issue that remains to be solved in the methoxycarbonylation reaction is the detailed mechanism by which the products are released - the so-called methanolysis step. There a several possibilities for this process, however, it is extremely difficult to obtain information on this from experiment as the reaction itself is incredibly fast. In these circumstances the use of computational modelling comes into its own, as this can readily provide information on the energies of the species involved in reactivity. The methanolysis reaction is, however, very complicated and is strongly dependent on the precise nature of the reacting species and the nature of the solvent being used. To obtain reliable modelling data these factors must be taken into account, a fact that makes the task of modelling these systems very challenging.This proposal seeks to use high level computational modelling to assess the mechanism of the methanolysis on the simplest methoxycarbonylation system - ethene/CO/MeOH - and the most effective Pd catalysts. Our approach will be to employ hybrid calculations where the catalyst and reacting molecules are dealt with at a high level of theory (density functional theory) but the solvent molecules (many 10s or hundreds) are treated at a lower level of theory based on classical force fields. Through this approach the effect of the solvent on the reactivity at the Pd catalyst will be taken into account and we aim to provide extremely reliable data to define the preferred mechanism. We will test our approach by comparing with an alternative catalyst which displays a different reactivity, thus giving a stringent test of our modelling approach.Once we have defined the correct way to treat these complicated reactions - as well as the mechanism by which methanolysis occurs - we will be in a position to tackle the new reactions of vinyl acetate and butadiene. We hope to provide sufficient insight into these processes that experimental chemists will be able to design new improved catalysts for more efficient methoxycarbonylation of these feedstocks on an industrial scale.

Soft matter and functional interfaces are ubiquitous! Be it manufactured plastic products (polymers), food (colloids), paint and other decorative coatings (thin films and coatings), contact lenses (hydrogels), shampoo and washing powder (complex mixtures of the above) or biomaterials such as proteins and membranes, soft matter and soft matter surfaces and interfaces touch almost every aspect of human activity and underpin processes and products across all industrial sectors - sectors which account for 17.2% of UK GDP and over 1.1M UK employees (BIS R&D scoreboard 2010 providing statistics for the top 1000 UK R&D spending companies). The importance of the underlying science to UK plc prompted discussions in 2010 with key manufacturing industries in personal care, plastics manufacturing, food manufacturing, functional and performance polymers, coatings and additives sectors which revealed common concerns for the provision of soft matter focussed doctoral training in the UK and drove this community to carry out a detailed "gap analysis" of training provision. The results evidenced a national need for researchers trained with a broad, multidisciplinary experience across all areas of soft matter and functional interfaces (SOFI) science, industry-focussed transferable skills and business awareness alongside a challenging PhD research project. Our 18 industrial partners, who have a combined global work force of 920,000, annual revenues of nearly £200 billion, and span the full SOFI sector, emphasized the importance of a workforce trained to think across the whole range of SOFI science, and not narrowly in, for example, just polymers or colloids. A multidisciplinary knowledge base is vital to address industrial SOFI R&D challenges which invariably address complex, multicomponent formulations. We therefore propose the establishment of a CDT in Soft Matter and Functional Interfaces to fill this gap. The CDT will deliver multidisciplinary core science and enterprise-facing training alongside PhD projects from fundamental blue-skies science to industrially-embedded applied research across the full spectrum of SOFI science. Further evidence of national need comes from a survey of our industrial partners which indicates that these companies have collectively recruited >100 PhD qualified staff over the last 3 years (in a recession) in SOFI-related expertise, and plan to recruit (in the UK) approximately 150 PhD qualified staff members over the next three years. These recruits will enter research, innovation and commercial roles. The annual SOFI CDT cohort of 16 postgraduates could be therefore be recruited 3 times over by our industrial partners alone and this demand is likely to be the tip of a national-need iceberg.

Atomistic structural, electronic and chemical models are the basis of modern material science, with data acquired under regular high vacuum conditions by analysis of mainly static specimens. However, the properties and hence functionality of many materials crucially depend on the environmental conditions to which they are exposed. Accordingly, relevant analyses of structure, composition and properties need to be conducted under controlled continuous dynamic conditions and the vision of this project is to enable and fully integrate the capabilities needed to accomplish these goals to understand nanomaterial-environment interactions, and ultimately to create nanomaterials by design. The overarching vision of this proposal is to fill the need for the fully integrated nanomaterials analysis with single atom sensitivity under dynamic process conditions in environmental conditions. The aim is to provide the state of the art tool available to UK research community to address the outstanding materials problems that underpin a number of EPSRC research themes from manufacturing the future to health and environment. Fully in situ and operando operations are needed to ensure the integrity of sample data. In practice this extends from sample synthesis or activation, through the ensuing operations, reactions or other processes or tests. Hence, resources are sought to establish a state-of-the-art, aberration corrected STEM instrument (200 to 40 kV) with 0.08 nm image resolution and comprehensive analytical functions for chemical and electronic state analysis with electron energy loss spectroscopy (EELS), related imaging filter (GIF), direct electron detection, and elemental analysis with a transformational high sensitivity (and acceptance angle) silicon drift detection (SDD) energy dispersive x-ray (EDX) spectrometer. The new instrument will be modified at York to include added unique functionalities, along the lines of the research led by the group. Methods and some hardware will be transferred from the original proof-of-concept and aged (2005) first generation instrument at York. The advantages of the open aperture 'gas-in-microscope' concept promoted at York are expected to be especially significant at the lower accelerating voltages of 80 and 40 kV to be available to reduce damage due to specimen-electron beam interactions. The new instrument and attendant expertise will be organised, actively promoted, operated and managed as a new national capability with connections to the national SuperSTEM and ePSIC laboratories, including CI representation from both organisations, for advice and user guidance and active assistance external promotion and strategic as well as tactical management. Wide networking will add to the framework for organising the new capability but will not exclude more ad hoc bilateral interactions; in part to promote the core science needed at the heart of such an 'organisation'. The scientific benefits of the proposed centre for excellence in environmental aberration corrected STEM will greatly contribute to the current research initiatives in the UK related to nanomaterials for energy applications, information technologies/internet of things, and catalysis. The key contribution will be in fundamental understanding of the nanomaterials environment interactions enables trough atomistic imaging and analysis of the dynamic processes that take place either during material fabrication or in action. The project will make a significant contribution to what the future of the UK and of the world will look like; through better understanding of societal, scientific, economic, and environmental challenges and opportunities.