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The production of conventional cross-linked polymer networks and their composites, i.e., thermosets and thermoset composites, was estimated to consume more than 40 billion kg of polymer in 2020. Unfortunately, thermosets cannot be melt-reprocessed into moderate- to high-value products because permanent crosslinks prevent melt flow. Three of many examples include rubber tires, disposed at a rate of ~300 million annually in the U.S. alone, polyurethane (PU) foam, and cross-linked polyethylene, with major economic and sustainability losses resulting because the spent materials are commonly landfilled or burned for energy. Here, I will report on research demonstrating the ability to employ simple one-step or two-step reactions to produce networks and network composites with dynamic covalent crosslinks that are robust at use conditions but allow for melt-state reprocessing at elevated temperature. Unique to our research group, we have developed several approaches that allow for melt-state reprocessing of addition-type polymer networks and network composites, including those synthesized directly from monomers containing carbon-carbon double bonds, such as those used in coatings and flooring, and those synthesized from polymer or combined polymer and monomer with both containing carbon-carbon double bonds, like materials used in tires and in cross-linked polyethylene. All approaches allow for full crosslink density recovery after multiple reprocessing steps. We have also demonstrated for the first time the ability to make PU and PU-like networks, e.g., polyhydroxyurethane and polythiourethane networks, reprocessable with full recovery of crosslink density. An "Achilles' heel" has been identified regarding the application of dynamic covalent networks, i.e., such networks are subject to creep at elevated or sometimes even room temperature, which is often highly undesirable. We have addressed this limitation in two ways. In one case, we add a fraction of permanent crosslinks to dynamic covalent networks. In a second class of systems, we employ dynamic chemistry with a sufficiently high activation energy, allowing for reprocessability at high temperature but with the dynamic chemistry essentially fully arrested well above room temperature, e.g., 70-80 degrees C. Implications of these studies for making major gains in the sustainability of polymer networks and network composites will be discussed.
The use of fossil resources and their negative environmental impacts has awakened the awareness of the petrochemical industry. Hereby, we are presenting some upstream industrial scalable and commercial solutions to process sustainable feedstocks, either biogenic or recycled, to produce drop-in hydrocarbons that can be converted into light olefins using the same assets and infrastructure currently established in the petrochemical industry (e.g. steam crackers), reducing the environmental impact of large-volume chemicals such as ethylene, propylene and benzene, which are the most demanded building blocks in the petrochemical value chain. Mass balanced certified co-processing of biogenic and recycled waste plastics as raw materials, are the key for the de-fossilisation of the petrochemical industry. Production of polypropylene (PP) using renewable feedstock can reduce the GHG above 80% or 3.8 kg CO2eq/kg in comparison with the fossil-based. For making a higher impact in the plastic industry, a full integration of the value chain is needed to guarantee allocation of the sustainable credits to targeted products. As a showcase, a collaboration project between partners in different parts of the value chain to produce biobased PP thermoformed plastic cups, is presented. As a result from this collaboration, PP cups with final properties identical in range to the traditional fossil were obtained and the renewable hydrocarbons could be identified in the product using C14. Drop-in solutions using renewable or recycled feedstock is paving the way in the petrochemical industry to obtaining sustainable products with low impact in the current downstream infrastructure.
Prof. Dr. Guralp Ozkoc was born in 1979 in Sinop, Turkey. He received his B.Sc. degree from Gazi University and his M.Sc. and Ph.D. (2007) degrees from the Polymer Science and Technology Department of Middle East Technical University (ODTU) in Ankara, Turkey. During his Ph.D. study, he researched as an intern-PhD at DSM in 2005 in The Netherlands. His Ph.D. thesis was on the "processing and characterization of short glass fiber and nanoclay reinforced ABS/PA6 blends". He also focused on the dispersion characteristics of nanoclays and polymer phases of ABS and PA6 concerning microcompounding conditions. After his Ph.D. graduation, he started as an Assistant Professor at Kocaeli University (KOU), Department of Chemical Engineering, in 2007. He founded the Plastics and Rubber Technology Research Group in 2008 at KOU, where 50+ MSc and Ph.D. students are actively conducting research. He supervised more than 35 M.Sc. and 15 Ph.D. theses in the last ten years. Furthermore, he chaired the Polymer Science and Technology Graduate Program for seven years, from 2011 to 2018. In 2019, he was promoted to a full-professorship position at Kocaeli University. In September 2020, he moved to The Netherlands to research additive manufacturing of polymer composites at TNO-Brightlands Material Center as a senior researcher. After working in this position for one year, he departed to Xplore Instruments BV/The Netherlands as Chief Technology Officer and General Manager. In 2021, Dr. Ozkoc started as a contract professor at Istinye University Department of Chemistry. He holds six patents and is the author of many international scientific papers and proceedings. Dr. Guralp Ozkoc's research interests are polymer compounding, polymer blending, composites and nanocomposites, elastomeric/rubber compounds, and biodegradable and biomedical materials.
Archetti, Damiano and Neophytou, Neophytos (2020)Thermoelectric properties of InA nanowires from full-band atomistic simulations. Molecules, 25 (22). 5350. doi:10.3390/molecules25225350 ISSN 1420-3049.
Buze, Maciej, Hudson, Thomas E. (Edward) and Ortner, Christoph (2020)Analysis of cell size effects in atomistic crack propagation. ESAIM: Mathematical Modelling and Numerical Analysis, 54 (6). pp. 1821-1847. doi:10.1051/m2an/2020005 ISSN 0764-583X.
Condorelli, Daniele and Szentes, Balázs (2020)Surplus bounds in Cournot monopoly and competition. Working Paper. Coventry: University of Warwick. Department of Economics. Warwick economics research papers series (WERPS), 1292 . (Unpublished)
Duchini, Emma, Simion, Stefania and Turrell, Arthur (2020)Pay transparency and cracks in the glass ceiling. Working Paper. Coventry: University of Warwick. Department of Economics. Warwick economics research papers series (WERPS) (1311). (Unpublished) 2b1af7f3a8