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Complex photonic structures in nature : from order to disorderOnelli, Olimpia Domitilla January 2018 (has links)
Structural colours arise from the interaction of visible light with nano-structured materials. The occurrence of such structures in nature has been known for over a century, but it is only in the last few decades that the study of natural photonic structures has fully matured due to the advances in imagining techniques and computational modelling. Even though a plethora of different colour-producing architectures in a variety of species has been investigated, a few significant questions are still open: how do these structures develop in living organisms? Does disorder play a functional role in biological photonics? If so, is it possible to say that the optical response of natural disordered photonics has been optimised under evolutionary pressure? And, finally, can we exploit the well-adapted photonic design principles that we observe in Nature to fabricate functional materials with optimised scattering response? In my thesis I try to answer the questions above: I microscopically investigate $\textit{in vivo}$ the growth of a cuticular multilayer, one of the most common colour-producing strategies in nature, in the green beetles $\textit{Gastrophysa viridula}$ showing how the interplay between different materials varies during the various life stages of the beetles; I further investigate two types of disordered photonic structures and their biological role, the random array of spherical air inclusions in the eggshells of the honeyguide $\textit{Prodotiscus regulus}$, a species under unique evolutionary pressure to produce blue eggs, and the anisotropic chitinous network of fibres in the white beetle $\textit{Cyphochilus}$, the whitest low-refractive index material; finally, inspired by these natural designs, I fabricate and study light transport in biocompatible highly-scattering materials.
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Laser Scattering for Fast Characterization of Cellulose Filaments / Laserspridning för Snabb Dimensionskarakterisering av CellulosafilamentKonstantinidou, Alexandra, Holmström, Saga, Hellberg, Susanna January 2022 (has links)
Cellulosananofibriller (CNFs) hör till naturens mest fundamentala byggstenar och förser naturliga material, såsom den yttre cellväggen i trä, med en otrolig styrka och styvhet. Genom att imitera träets arkitektur öppnas möjligheter upp för tillverkning av nya, biobaserade och lättviktiga strukturella material med mekaniska egenskaper som överskrider de för glasfiber, metaller och legeringar. Den ingenjörsmässiga utmaningen ligger i att framgångsrikt lyckas överföra de önskade mekaniska egenskaperna hos CNFs till filament som kan användas i material för dagligt bruk. Vid flödesfokuserad spinning av extraherade CNFs påverkar många parametrar den slutgiltiga funktionaliteten och kvaliteten hos de resulterande filamenten. För att optimera dessa processparametrar är mätning av de spunna filamentens dimensioner ett viktigt moment. Av särskilt intresse är filamentbredden, eftersom den är avgörande för de mekaniska egenskaperna. Karakterisering av filamentbredden är i dagsläget en mycket tidskrävande process där varje filament mäts manuellt i optiskt mikroskop. Det huvudsakliga målet med detta projekt är att effektivisera den nuvarande mätprocessen med avseende på både hastighet och noggrannhet med hjälp av laserspridning. I denna rapport visar vi på minst en halvering av nuvarande mättid vid användandet av en 3D-printad laseruppställning istället för ett optiskt mikroskop vid mätning av filamentbredd. Våra resultat indikerar att mätsäkerheten generellt är högre för lasermetoden jämfört med mikroskopin. Genomsnittliga standardavvikelser för mätvärden på tunnaste bredden från mikroskopi samt de två olika kurvanpassningsmetoderna vid lasermätning rapporteras vara 1.62, 0.85 (Curve fit) respektive 1.59 (Minima matching). Standardavvikelserna för tunnaste bredd korrelerar dock inte direkt mot metodernas noggrannhet eftersom de spunna filamenten uppvisar en stor variation i bredd längs med längden. En närmare jämförelse mellan mätvärden för matchade punkter på ideala och defekta filament demonstrerar att icke-uniforma och defekta filament påverkar mätnoggrannheten för laserspridningen negativt. Sammantaget stödjer våra resultat det faktum att ett tunnare filament resulterar i bättre upplösning och mindre mätfel vid mätning med laserspridning. Våra resultat visar på den stora potentialen för laserspridning som en mer effektiv mätmetod vid karakterisering av cellulosafilamentbredd. / Cellulose nanofibrils (CNFs) are one of nature’s most fundamental building blocks, providing incredible strength and stiffness to natural materials, such as the outer cell wall layer in wood. By mimicking the architecture of wood, possibilities opens up for the fabrication of new, biobased, light-weight structural materials with mechanical properties exceeding that of glassfibers, metals and alloys. However, the engineering challenge lies in successfully managing to translate the desirable mechanical properties of the CNFs into filaments that can be used in everyday life materials. Throughout the process of spinning the extracted CNFs into filaments, many factors and parameters affect the ultimate functionality and performance of the resulting filaments. Measuring the dimensions of the spun filaments is a crucial step in further optimizing process parameters. The width of the filament especially, impacts its mechanical performance. The characterization of the cellulose filament width is currently very time-consuming as each filament is manually measured using optical microscopy. The primary goal of this project is to make the current characterization process more effective, with respect to both accuracy and speed of measurement, by using laser scattering. In this report, we demonstrate a reduction by more than a half in measurement time using a 3D-printed laser scattering setup instead of an optical microscope when measuring filament width. Our results indicate that the certainty in measurement is generally higher for lase rscattering compared to optical microscopy. The mean standard deviations (SD) for the smallest widths estimated with optical microscopy and the two curve fitting methods used for the laser measurements are reported to be 1.62, 0.85 (Curve fit) and 1.59 (Minima matching) respectively. However, standard deviations for the thinnest width does not correlate directly to the accuracy of the methods since the spun filaments show a large variation in width along the length. A closer comparison between measurement values for matched points at ideal and non-uniform filaments demonstrate that the accuracy of the laser measurements are dependent on the uniformity of the filaments, with non-uniform filaments negatively impacting the accuracy. Our overall results supports the fact that a thinner filament gives a better resolution and smaller error when measuring with laser. Our results provide evidence for the great potential of laser scattering as a more efficient method for cellulose filament width determination.
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Emulsion polymerization in the presence of reactive PEG-based hydrophilic chains for the design of latex particles promoting interactions with cellulose derivatives / Polymérisation en émulsion en présence de chaînes polymères hydrophiles réactives à base de PEG pour la conception de particules de latex permettant des interactions avec des dérivés cellulosiquesGriveau, Lucie 07 December 2018 (has links)
Dans cette thèse, des particules de polymère fonctionnalisées en surface avec des groupes poly (éthylène glycol) (PEG) ont été synthétisées pour favoriser leur interaction avec les dérivés cellulosique via liaisons hydrogène intermoléculaires. Deux voies de synthèse ont été proposées pour obtenir ses composites cellulose/latex.La première voie est basée sur l'auto-assemblage induit par polymérisation (PISA) pour former des nanoparticules fonctionnalisées avant leur adsorption sur un substrat cellulosique. La PISA tire profit de la formation de copolymères blocs amphiphiles dans l'eau en combinant la polymérisation en émulsion avec les techniques de polymérisation radicalaire contrôlées (RDRP). Ces dernières sont utilisées pour synthétiser des polymères hydrophiles agissant à la fois comme précurseur pour la polymerization en émulsion d'un monomère hydrophobe, et comme stabilisant des particules de latex obtenues. Deux techniques de RDRP ont été étudiées : les polymérisations RAFT et SET-LRP. Des polymères hydrophiles à base de PEG de faible masse molaire ont été synthétisés en utilisant ses deux techniques qui sont ensuite utilisés pour la polymérisation d'un bloc hydrophobe dans l'eau. Le transfert de l'agent de contrôle au site de la polymérisation était difficile en utilisant la SET-LRP en émulsion, conduisant à la formation de larges particules. En utilisant la RAFT en émulsion, des particules nanométriques ont été obtenues, avec un changement morphologique observé en fonction de la taille du segment hydrophobe, puis adsorbées sur des nanofibrilles de cellulose (CNF).La seconde voie utilise la polymérisation en émulsion classique réalisée en présence de nanocristaux de cellulose (CNC) conduisant à une stabilisation Pickering des particules de polymère. L'interaction cellulose/particule est assurée grâce à l'ajout d’un comonomère à type PEG. Une organisation a été visualisé dans laquelle plusieurs particules de polymère recouvrent chaque CNC / In this thesis, polymer particles surface-functionalized with poly(ethylene glycol) (PEG) groups were synthesized to promote their interaction with cellulose derivatives via intermolecular hydrogen bond. Two synthetic routes were proposed to obtain such cellulose/latex composites.The first route was based on the polymerization-induced self-assembly (PISA) to form functionalized polymer nanoparticles prior to adsorption onto cellulosic substrate. PISA takes advantage of the formation of amphiphilic block copolymers in water by combining emulsion polymerization with reversible-deactivation radical polymerization (RDRP) techniques. The latter were used to synthesize well-controlled hydrophilic polymer chains, acting as both precursor for the emulsion polymerization of a hydrophobic monomer, and stabilizer of the final latex particles. Two RDRP techniques were investigated: reversible addition-fragmentation chain transfer (RAFT), and single electron transfer-living radical polymerization (SET-LRP). Low molar mass PEG-based hydrophilic polymers have been synthesized using both techniques, used for the polymerization of a hydrophobic block in water. The transfer of controlling agent at the locus of the polymerization was challenging for SET-LRP in emulsion conditions leading to surfactant-free large particles. Nanometric latex particles were obtained via RAFT-mediated emulsion polymerization, with morphology change from sphere to fibers observed depending on the size of the hydrophobic segment, which were then able to be adsorbed onto cellulose nanofibrils (CNFs).The second route used conventional emulsion polymerization performed directly in presence of cellulose nanocrystals (CNCs) leading to Pickering-type stabilization of the polymer particles. Cellulose/particle interaction was provided thanks to the addition of PEG-based comonomer. Original organization emerged where CNCs were covered by several polymer particles
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