Title Promoter Affiliations Abstract "Biobased Coatings" "Patrick Cosemans" "Smart Coating" "In order to meet changing consumer requirements in terms of origin and sustainability and European regulations, the coating industry and its users need to adapt. Although everyone in the value chain is convinced of the usefulness of bio-based coatings, their introduction is stagnating. European research and a survey of Flemish companies show that there are various reasons for this delayed breakthrough. However, there are immense opportunities to develop new bio-based coatings thanks to the increasing supply of new bio-based building blocks from (non-food) biomass. Some bio-based coatings have even better or wider application possibilities than fossil-based coatings.Often, the way the coating is applied appears to have a greater impact on the proper functioning of the coating layer than its composition. Although there is a will among distributors and developers, there is insufficient know-how about the processing and application of bio-based coatings and the start-up to process new bio-based raw materials is complex, time consuming and expensive. Moreover, it is impossible to replace certain chemicals on a 'one-to-one' basis and the unfamiliarity with the composition of bio-coatings results in insufficient insight into the possibilities and bottlenecks during their development. Internationally, research focuses on the development of building blocks and not on the validation of bio-coating formulations and their application." "CycloPUR – Fundamental insights in reversible polymerization of polyurethanes." "Lukasz Pazdur" "Intelligence in PRocesses, Advanced Catalysts and Solvents (iPRACS), Biochemical Wastewater Valorization & Engineering (BioWaVE)" "Polyurethanes (PU) are versatile group of polymers, being used increasingly in diverse applications; for instance in mattresses, building foams, automotive and adhesives. PU is a cross-linked polycondensation polymer, in which polyols (polyhydroxyl alcohols) react with highly reactive diisocyanates. As a thermoset (they do not have a melting point), PU is difficult to recycle, and the current state-of-the-art mechanical recycling results in low-value materials. Nonetheless, chemolysis (chemical depolymerization) has been explored since decades as an alternative, yet was only commercially developed for polyol recovery. The absence of a working technology for recovery of diisocyanate derivatives is largely due to the complexity of these molecules, and a lack of knowledge regarding their chemical fate in a chemolysis process. The proposed STIMPRO aims at understanding how various isocyanate derivatives are formed, and how they react upon alcoholysis, by experiments using model monomers. This knowledge, together with experimental and computational insights in mixing/solubility, will be exploited to create a bottom-up chemolysis process for model polyurethanes. The outcome of the proposed study will be used in subsequent chemolysis of realistic waste polyurethanes, with recovery of both monomers as significant technological novelty. Additionally, the resulting knowledge may be transferred in the future formulation of new polyurethanes with biobased alternative monomers" "Design and synthesis of organic semiconductors for nearinfrared photodetection with bulk heterojunction organic cavity devices" "Wouter MAES" "Materials Chemistry, Materials Physics, Organic and Bio-polymer Chemistry" "Blending organic electron donors and acceptors yields intermolecular charge transfer (CT) states with additional optical transitions below their optical gaps. In organic photovoltaics, such CT states play a crucial role and they limit the operating voltage. Due to its extremely weak nature, direct intermolecular CT absorption often remains undetected and unused for photocurrent generation. However, the negligible external quantum efficiency in the spectral region of CT absorption can substantially be increased through the use of optical cavities, allowing narrow-band detection with substantial quantum efficiencies and resonance wavelengths extending into the nearinfrared (NIR). The broad spectral tunability via simple variation of the cavity thickness makes this novel, flexible and potentially visibly transparent device principle highly suitable for integrated low cost (spectroscopic) NIR photodetection. Despite the high promises of this innovative concept, dedicated frontier research is required to further optimize the device output and to elucidate its fundamental limitations. In my PhD project, the emphasis will be on the development of high-quality (high-HOMO) electron donor and (low-LUMO) electron acceptor materials and their (basic) cavity device analysis, while more in-depth device, photophysics and blend nanomorphology studies will be conducted in collaboration with partner groups, with the final goal to unravel structure-solution processing-photodetector relations." "Development of high-performance ultra-low bandgap copolymers for near-infrared photodetectors." "Wouter MAES" "Materials Chemistry, Engineering Materials and Applications, Organic and Bio-polymer Chemistry" "Due to their application in night and thermal vision systems, infrared image sensors are truly imaginative. To date, they are produced via the so-called hybrid technology, in which both the detector and the electronic readout are prepared separately and then interconnected at the pixel level. Obviously, this is a time-consuming process, resulting in low throughput and thus high cost, limiting widespread use (e.g. smartphones). A monolithic approach with direct deposition of the detectors on top of the electronic readout can provide a solution. Attempts to apply this technology to the current inorganic low bandgap absorbers were, however, not very successful due to compatibility issues. In this respect, organic semiconductors are very interesting, since they are compatible with almost all surfaces. For UV-VIS light detection, it is already proven that organic photodetectors (OPD's) can match and even surpass the performance of inorganic photodetectors. However, these organic materials generally show limited absorption in the near- IR region. In this project, we aim at a noteworthy contribution to the above challenge by fundamental scientific studies on the photoactive (p-type) materials required for near-IR OPD's. Synthetic procedures toward ultra-low bandgap copolymers will be carefully optimized, with particular attention for material purity and specific material/photodiode properties (IR absorption, miscibility with the n-type material, high mobility and low dark current)." "Bio-LCCMs - long chain condensation monomers." "Serge Tavernier" "Biochemical Wastewater Valorization & Engineering (BioWaVE)" "The proposed research aims at developing (new) affordable, valuable long chain α,ω bifunctional monomers for condensation reactions, sustainably produced, and provide demonstration samples, in view of filing a patent application with parallel industrial valorization. The envisioned monomers will yield new materials, polymers in particular, with unprecedented physicochemical, thermal and mechanical properties compared to existing short (max. C10 chains) α,ω bifunctional condensation monomers. Moreover, the newly developed materials are expected to be biodegradable, and offer opportunities for chemical recycling. To date, monomers comparable to our envisioned monomers can only be produced at low carbon efficiencies and high economic and environmental cost. In contrast, we propose a new synthesis route, complying to green chemistry principles, yielding long (C18+) α,ω bifunctional monomers, as well as their asymmetric versions, and a synthesis route for chain length extension and even doubling. The latter two processes were thus far (industrially) neither known nor feasible. Monomers with such long or doubled chain length were unprecedented to date. The feasibility of our proposed synthesis route has already been demonstrated by preliminary experiments. The performance of such new C18 polyester structures will be benchmarked against that of traditional (short chain) alternatives. A second phase focuses on longer (C18+) chains. In the latter case an ether molecule from two fatty chains, terminated on both sides, will be obtained. The total length of the chain between two functional groups is intended to be long, meaning at least 18 atoms. We hypothesize that the presence of the ether-oxygen internally does not fundamentally alter the chain structure, resulting in similar properties as an equivalent homogeneous carbon chain. The properties of the associated newly obtained oligomers and polymers will be assessed, and the data obtained will serve as examples for a patent application. In a third phase the production process will be optimized (e.g. with respect to cost structure) for a selection of monomers, i.e. those with the highest industrial demand. These monomers will be produced and supplied in larger quantities as demonstration samples, in light of prompting industrial valorization. First cost estimates will be made." "Sugar-based chemicals and Polymers through Innovative Chemocatalysis and engineered Yeast (SPICY)" "Materials Chemistry, Organic and Bio-polymer Chemistry" "SPICY's main aim is to provide chemical industry with new or optimized processes to convert sugars into added value compounds, i.e. both drop-ins and novel biobased chemicals. Two complementary lines are hereto developed in parallel, one focusing on biotechnology based on improved yeast-strains and one based on chemocatalytic routes. Both will aspire to meet industrial standards of productivity, titer, yield and selectivity, to safeguard potential economic benefit and future industrial valorization. Most of the target chemicals are (potential) monomers for biobased plastics, hence, a second aim of SPICY is to deliver proof-of-concept of their usefulness by targeting novel and functional polymeric materials, typically not found in the current oil-based valorization chain. The innovation is thus to be achieved both in terms of processes and products in the context of furthering the Flemish biobased value chain." "Bonus external PhD Sam Gielen" "Wouter MAES" "Materials Chemistry, Organic and Bio-polymer Chemistry" "When a Hasselt University doctoral student with funds from the BOF doctoral fund or from the BOF New Programmes doctoral fund acquires additional funding within the first twelve months of the fellowship, the freed up funds flow back into the Doctoral Fund or the New Programmes doctoral fund. These funds can then be used for extra fellowships. The research group within which the scholarship student is active will receive a one-off sum of 10,000 euros." "Fullerene-free bulk heterojunction blends for organic electronics" "Wouter MAES" "Materials Chemistry, Organic and Bio-polymer Chemistry" "Over the past decades, organic semiconductors have become increasingly popular because of their ability to combine the electronic properties of semiconducting materials with the mechanical and chemical versatility of organic compounds. As such, they have been applied in multiple electronic devices. In the field of organic photovoltaics (OPVs), the bulk heterojunction (BHJ) photoactive layer concept has surely demonstrated its value, as power conversion efficiencies over 11% have recently been reported. State of the art organic photodetectors (OPDs) consist of the same donor:acceptor BHJ architecture. For a long time, fullerenes have been the dominating class of electron acceptor molecules in both types of devices, but recent noteworthy results have caused a paradigm shift to alternative non-fullerene systems, with considerable advantages in terms of cost, tunability, absorptivity and stability. Despite the impressive progress in solar cell efficiency, a detailed understanding of structure - BHJ morphology - device property relations for novel fullerene-free blends remains noticeably absent. Therefore, this project envisages a detailed fundamental understanding of how molecular engineering of alternative acceptor molecules influences the BHJ blend morphology and thereby the performance of OPVs and OPDs. To this extent, a set of very complementary blend analysis techniques will be employed. The (thermal) stability of the novel blends will be investigated as well." "Porphyrinoid materials for near-infrared organic photodetectors" "Wouter MAES" "Organic and Bio-polymer Chemistry" "The eminent threat of terrorism has caused safety and surveillance to become increasingly important aspects in our daily lives. Infrared image sensors can enhance our security by enabling night vision, thermal imaging and chemical sensing applications. To date, the so-called hybrid technology is used for these image sensors, in which both the photodetector (PD) and the electronic readout are prepared separately and then interconnected at the pixel level. Obviously, this is a time-consuming process, resulting in low throughput and thus high cost. A monolithic approach is hence more attractive. Attempts to apply this technology to the state of the art inorganic low bandgap absorbers are, however, not very successful because of compatibility issues. In this respect, organic semiconductors are much more appealing. As Nature itself has developed porphyrins as light-harvesting chromophores, it feels natural to pursue PD systems based on similar molecules. Moreover, the versatility of porphyrinoid chemistry allows to extend their absorption to the near-infrared (NIR). In this project I will prepare advanced push-pull type porphyrinoid materials with very low bandgaps with a particular emphasis on corroles, contracted porphyrin derivatives with a specific coordination behavior and distinct photophysical features by optimized synthetic sequences and I will evaluate them in NIR organic PDs, with the specific aim to prepare devices competitive with their inorganic counterparts." "Design and development of biodegradable polymer/ gold nanorod hybrid nano carriers for photothermal cancer therapy : Evaluation by (non-)linear optical methods." "Dirk VANDERZANDE" "Materials Physics, Bio-Physics, Organic and Bio-polymer Chemistry" "The use of nanoparticles (NPs) in medicine has seen a tremendous rise in interest owing to their vast potential as diagnostic and therapeutic agents. One such instance is the use of nanomaterials for photothermal therapy (PTT) to treat conditions like cancer. PTT is a technique in which localized hyperthermia is induced by converting light energy to heat, to selectively destroy the diseased tissue. This method has been shown to be very promising as it is minimally invasive and presents reduced complications as compared to chemotherapy or surgery. Gold nanorods (GNRs) have been used before as the PTT agent. This project deals with a novel way of delivering GNRs to biological cells by encapsulation of an ensemble of GNRs in a biodegradable polymeric nanocarrier. The PTT efficacy of this new approach will be compared with the equivalent dose of individual unencapsulated GNRs. A systematic analysis of cellular uptake, intracellular dynamics and localization, and the protein corona (adsorbed protein layer) formed in relevance to the movements of the nanoparticles inside biological cells will be undertaken. Thereto, advanced optical imaging techniques combining incoherent fluorescence and coherent second harmonic signals will be developed. This research will ultimately result in a better understanding about the design and use of GNRs in the human body for the purpose of PTT, and will form a basis for future in vivo."