This diploma thesis focuses on the problematics of preparation of biodegradable starch based packaging. The aim of the thesis is to optimize the preparation and verify the characteristics for further adaptation and production technologies. The films consisted of starch, PVA and glycerol. Four types of starches, three types of PVA and different ratios of glycerol were tested. Films were prepared by casting with glycerol as a plasticizer, instead of distilled water, to reduce the energy cost of the preparation. The mechanical properties of the films were tested as well. The experimentally determined values of elongation at break and tensile strength of the wheat starch films were compared with a semiempirical model. Results revealed that the preparation of thermoplasticization of starch with glycerol leads to a considerable increase in elongation at break but at the same time to a marked decrease in tensile strength compared to the preparation from solution. The rheological properties of the prepared films were also investigated. Infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to study the structure of the films.

Le glycérol est une molécule bio-sourcée, abondamment disponible, issue de la saponification des corps gras et de la transestérification des huiles végétales. Les travaux portent sur l'utilisation du glycérol comme base structurale de cœurs de dendrimère, en particulier par addition d'oxa-Michael sur des dérivés acryliques. La fonctionnalisation en surface de dendrimères par des motifs imidazolium est explorée afin d’obtenir un dendrimère liquide ionique (DLI) aux propriétés thermosensibles. Le chapitre bibliographique est consacré dans une première partie, aux méthodes de synthèse de dendrimère mettant en jeu des dérivés acryliques et à leurs applications et dans une seconde partie, aux travaux consacrés à l'addition oxa-Michael d'alcools sur des dérivés acryliques. Le deuxième chapitre porte sur les synthèses, à partir du glycérol, de la base structurale du cœur de dendrimère. La réaction d’acylation du glycérol par le chlorure d’acryloyle est présentée ainsi que les différentes constructions de dendrimères poly(estersulfure) à partir du triacrylate de glycérol. L’addition nucléophile du glycérol sur l’acroléine, l’acrylamide, des acrylates et l’acrylonitrile a été étudiée. Avec les acrylates, la réaction d'addition nucléophile est en compétition avec la réaction de transestérification, à l’exception de l'acrylate de t-butyle résistant en milieu basique. Avec l’acrylonitrile, la synthèse du 1,2,3-tricyanoéthylglycéryléther a pu être menée sans solvant, en 5 heures à température ambiante, en présence d’un catalyseur peu coûteux (la soude 4 mol %) avec un rendement de 88% et une pureté de 99% sans méthode de purification. Les intermédiaires de réaction mono- et di-cyanoéthylglycéryléther ont été caractérisés et ont permis un suivi cinétique de la réaction. La synthèse de dendrimères poly(amidoamine) à partir du 1,2,3-tricyanoéthylglycéryl éther fait l’objet du troisième chapitre : synthèse des générations G0 à G2,5, caractérisation des dendrimères. Des défauts de structure dus à une cyclisation intramoléculaire ont été mis en évidence par HRMS pour les générations entières et les dendrimères de demi-génération Gn+5 (n entier) sont purifiés par colonne chromatographique. Différentes voies de synthèse pour l’obtention d’un DLI à termini imidazolium sont présentées / Glycerol is a bio-based molecule, abundantly available, from the saponification of triglyceride and the transesterification of vegetable oils. The work described in this PhD thesis concerns the use of glycerol as structural base of dendrimer's core, in particular by oxa-Michael addition on acrylic derivatives. The surface functionalization of dendrimers by imidazolium units is explored in order to obtain an ionic liquid dendrimer (DLI) with thermosensitive properties. In the first part, the bibliographic chapter presents the methods of dendrimers synthesis involving acrylic derivatives and their applications and, in a second part, the work introduces the oxa-Michael addition of alcohols to acrylic derivatives. The second chapter deals with the synthesis of the structural base of the dendrimer core from glycerol. The reaction of acylation of glycerol with acryloyl chloride is presented as well as the various constructions of poly(estersulfide) dendrimers from glycerol triacrylate. The nucleophilic addition of glycerol to acrolein, acrylamide, acrylates and acrylonitrile has been studied. With the acrylates, the nucleophilic addition reaction is in competition with the transesterification reaction, with the exception of t-butyl acrylate, resistant in basic medium. With acrylonitrile, the synthesis of 1,2,3-tricyanoethylglycerylether was carried out without solvent in 5 hours at room temperature in the presence of an inexpensive catalyst (4 mol% sodium hydroxide) in a yield of 88% and purity of 99% without purification method. The mono- and di-cyanoethylglycerylether reaction intermediates were characterized and allowed kinetic monitoring of the reaction. The synthesis of poly(amidoamine) dendrimers from 1,2,3-tricyanoethylglycerylether is the subject of the third chapter: synthesis of generations G0 to G2,5 and characterization of dendrimers. The defects in the structure due to intramolecular cyclization have been demonstrated by HRMS for generations Gn and the half-generation dendrimers Gn+5 (n=0, 1, 2) were purified by chromatographic column. Several routes of synthesis for the synthesis of DLI with imidazolium termini are presented

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Microfluidic flow devices coupled with quantitative Raman spectroscopy are able to provide a deep insight into the reaction mechanism and kinetics of electrocatalytic reactions. With a microfluidic flow device made with glass microscope slides and polymer building blocks, the feasibility of this technique was examined by methanol electrooxidation reaction with a Pt working electrode. Pre-calibration of the Raman peak area was done with solutions of known concentrations of methanol and its major oxidation product, i.e., formate, which enabled the time-dependent Raman spectra taken during the reaction to be converted to time-dependent concentrations. These were interpreted in terms of a model with one-dimensional convection and the reaction kinetics. An improved version of this technique was then applied to a comparative study of different alcohols with Ni-based electrodes. This showed the production of formate as the major product from the oxidation of alcohols with vicinal OH groups, leading to the discovery that C-C bond dissociation is a major reaction pathway for vicinal diols and triols if Ni electrocatalysts are used. It is also suggested that the cleavage of C-C bonds is the rate-determining step. The potential use of printed circuit boards (PCB) in the next generation of a novel microfluidic device was explored, as PCB have advantages over regular electrochemical microfluidic substrates, such as simpler electrode fabrication strategies, more wiring layers, and customization of size and shape of electrodes. Pretreatments and electrodeposition protocols of nickel, silver, palladium and platinum on PCB were successfully developed, together with four types of PCB-based microfluidic devices designed with an open-source PCB design software. This work establishes a new electrochemical microfluidic platform for online and in-situ monitoring of electrocatalytic reactions, which can quickly determine the reaction mechanism and kinetics. / Graduate

In 2014 SÖRAB constructed a continuous biological treatment system (KBR) to handle leachate waterfrom the landfill at the facility in Löt, north of Stockholm. The KBR is mainly focused on removal ofammonium nitrogen which would otherwise be released in to the recipient and contribute toeutrophication and damage to the environment. This project has focused on replacing the currentcarbon source in the process Brenntaplus VP1 and evaluating the efficiency of denitrification andeconomy of transitioning to a new carbon source. The carbon sources glycerol and ethanol wereevaluated and compared to Brenntaplus VP1 for the denitrification efficiency and microbial profile.The experiments were performed in laboratory conditions and in pilot scale using leachate water fromLöt. The reduction of ammonia was evaluated by chemical precipitation, addition of carbon sources bymeasuring ammonia-N and nitrate-N under aerobic (nitrification) and anaerobic (denitrification)conditions. The combination of ethanol and glycerol showed an enhanced denitrification and increasedmicrobial community both in lab and pilot scale studies with reduced hydraulic retention time. Therate of nitrate reduction was 0.23 mgNO3-N 1 -1 h -1 for ethanol/glycerol compared to 0.12-0.17mgNO 3- -N 1 -1 h -1 for Brenntaplus VP1 in pilot scale. The results indicate that using ethanol, glycerolor a mix of the two as a substitute for Brenntaplus VP1 is viable. This has been based on laboratoryand pilot scale studies. Each of the carbon sources examined during this project have showed a uniqueimpact on the process and its parameters such as: denitrification rate, microbial density and microbialcomposition. The carbon sources had an impact with temperature fluctuation and faster denitrificationcompared to the conventional KBR system. This implies that the carbon sources tested in this projectcan be advantageous and beneficial for Sörab depending on the carbon source availability and theseasonal variations. / Under 2014 konstruerade SÖRAB ett kontinuerligt biologiskt reningsverk (KBR) för att hanteralakvatten från deponin för ickefarligt avfall vid anläggningen i Löt, norr om Stockholm. KBR ärfrämst konstruerad för rening av ammoniumkväve som annars skulle släppas ut till recipienten ochbidra till övergödning och skador på miljön i området. Detta projekt har fokuserat på att ersätta dennuvarande kolkällan Brenntaplus VP1 som används i processen och utvärdera effektiviteten idenitrifieringen samt ekonomin vid övergång till en ny kolkälla. Kolkällorna glycerol och etanol varde kolkällor som valdes för utvärdering i detta projekt, dessa jämfördes med Brenntaplus VP1 i desseffekt på denitrifikationseffektivitet och mikrobiell sammansättning under laboratorieförhållanden ochi pilotskala. Möjligheten att reducera ammoniumkoncentrationen i lakvattnet utvärderades genomkemisk fällning och genom mätning av ammoniumkväve och nitratkväve under aeroba (nitrifikation)och anaeroba (denitrifikation) förhållanden. Kombinationen av etanol och glycerol indikerade enförbättrad denitrifikation och ökad mikrobiell densitet både i laboratorie- och pilotskala med reduceradhydraulisk retentionstid. Nitratreduktionshastigheten var 0,23 mgNO 3- -N 1 -1 h -1 för blandningen avetanol/glycerol jämfört med 0,12 - 0,17 mgNO 3- -N 1 -1 h -1 för Brenntaplus VP1 i pilotskala. Resultatenindikerar att användning av etanol, glycerol eller en blandning av de två har goda förutsättningar föratt ersätta Brenntaplus VP1. Var och en av de tre kolkällorna som undersöktes under detta projekt harvisat en unik inverkan på processen och dess parametrar såsom: denitrifikationshastighet, mikrobielldensitet och mikrobiell sammansättning. Genom att byta kolkälla i KBR kan prestandan ökas genomatt minska den hydrauliska retentionstiden samtidigt som systemet tycks bli mindre känsligt förtemperatursvängningar. Kolkällorna som utvärderats i detta projekt kan därför vara fördelaktiga för SÖRAB beroende på dess tillgänglighet och pris.

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第25019号 / 人博第1097号 / 新制||人||257(附属図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 小松 直樹, 教授 津江 広人, 教授 藤田 健一, 准教授 Zhao Li / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

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