This diploma thesis deals with the evaluation of changes in properties of an antifreeze heat transfer liquids based on glycols used in real solar thermal system. Emphasis is placed on the use of non-toxic substances, which include propane-1,3-diol.

L’objectif du projet est de préparer de nouveaux copolyéthers hydrophiles biosourcés, non ioniques, pour des applications cosmétiques proches de celles du polyéthylène glycol (PEG). Le polytriméthylène éther glycol (PTEG), dont la structure ressemble à celle du PEG, a été synthétisé par polymérisation du 1,3-propanediol biosourcé (PDO) en catalyse acide. Parmi les catalyseurs testés, l’acide sulfurique est le plus approprié pour polymériser le PDO sans dégradation excessive. Pour augmenter la solubilité du PTEG dans l’eau, des copolymères associant des unités PDO et des unités hydrosolubles type isosorbide et glycérol ont été envisagés. Ainsi, nous avons montré que l’éthérification en catalyse acide entre l’isosorbide et le PDO (ou le PTEG) conduit à de nouvelles structures de copolyéthers que nous avons finement caractérisés par RMN et spectrométrie de masse. Ces copolyéthers ont des extrémités préférentiellement constituées d’unités isosorbide, du fait d’un différentiel de réactivité entre le PDO et l’isosorbide. En revanche, l’éthérification du PDO et du glycérol par catalyse à l’acide sulfurique ou par catalyse basique n’a pas abouti. En effet, dans le premier cas, on observe une très forte dégradation voire une réticulation et dans le deuxième cas, seule l’homopolymérisation du glycérol est observée. Pour compléter, la réaction entre du carbonate de glycérol et un oligomère de PTEG donne les dérivés souhaités, même si le milieu réactionnel reste riche en polyglycérol libre. Les produits les plus prometteurs de l’étude sont des copolyéthers de PDO et d’isosorbide, d’environ 600 g/mol, obtenus par éthérification en catalyse acide. Ces nouveaux copolyéthers ont des bouts de chaînes constitués d’unités isosorbide, sont hydrosolubles et ont une stabilité thermique améliorée par rapport aux PTEG. / The aim of this project is to prepare some new hydrophilic biobased copolyethers for cosmetic applications, similar to those of polyethylene glycol (PEG). Synthesis of polytrimethylene ether glycol (PTEG) which has a chemical structure close to the PEG was studied by polymerizing 1,3-propanediol (PDO) with sulfuric acid as catalyst. This acid catalyst is appropriate to promote the polymerization of PDO without excessive degradation. We tried to increase the solubility of PTEG in water by combining to PDO units hydrophilic monomers, such as isosorbide and glycerol, to the PDO units. We showed that etherification of isosorbide and PDO (or PTEG), in the presence of acid catalyst, gives new copolyethers structures, deeply characterized by NMR and mass spectroscopy. These copolyethers are preferably ended by isosorbide units due to different reactivity between isosorbide and PDO. The etherification of the PDO and glycerol with sulfuric acid results in a cross-linked and degraded product. Basic catalytic route favored the polymerization of glycerol on itself rather than the etherification on PDO units. We also grafted glycerol carbonate on PTEG oligomer but obtained a complex composition mixture rich in polyglycerol. The most promising products of the study are PDO and isosorbide copolyethers with a molar mass of 600 g/mol, obtained by etherification with sulfuric acid as catalyst. These copolyethers have chain ends constituted by isosorbide units, are water soluble and have a higher thermal stability compared to PTEG.

Orientador: Jonas Contiero / Resumo: A contaminação ambiental causada por compostos orgânicos é um importante problema que afeta solos e água superficiais. Para reduzir ou remover esses poluentes, os locais contaminados são geralmente tratados com métodos físicos e químicos. No entanto, a maioria dessas técnicas de remediação é custosa e geralmente leva à remoção incompleta e à produção de resíduos secundários. A nanotecnologia consiste na produção e aplicação de estruturas extremamente pequenas, cujas dimensões estão na faixa de 1 a 100 nm, neste cenário a nanopartícula de ferro zero valente representa uma nova geração de tecnologias de remediação ambiental. É não tóxica, abundante, barata, fácil de produzir, e seu processo de produção é simples. No entanto, a fim de diminuir a tendência de agregação, a nanopartícula de ferro zero é frequentemente revestida com surfactantes. A maioria dos surfactantes é quimicamente sintetizado a partir de fontes petroquímicas, eles são persistentes ou parcialmente biodegradáveis, enquanto oferecem baixos riscos à saúde humana, esses compostos podem prejudicar plantas e animais. Para diminuir o uso de métodos químicos, a síntese e estabilização verde de nanomateriais metálicos apresentam-se como uma opção menos perigosa ao meio ambiente. Os biossurfactantes podem potencialmente substituir qualquer surfactante sintético, eles são compostos extracelulares produzidos por microrganismos, como bactérias, e cultivados em diferentes fontes de carbono, podendo ser substratoshidrofílico... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Environmental contamination caused by organic compounds is the most important challenge that affects a huge number of soils and water surfaces. To reduce or remove these pollutants, contaminated sites are usually treated using physical and chemical methods. However, most of these remediation techniques are expensive and commonly lead to incomplete removal and to the production of secondary wastes. Nanotechnology is the production and application of extremely small structures, whose dimensions are in the range of 1 to 100 nm and Nanoscale zero-valent iron represents a new generation of environmental remediation technologies, is non-toxic, abundant, cheap, easy to produce, and its reduction process requires little maintenance. Nonetheless, in order to diminish the tendency of aggregation, nanoscale zero-valent iron is often coated with surfactants. Most surfactants are chemically synthesized from petrochemical sources, they are slowly or partially biodegradable, while offer low harm to humans, such compounds can influence plants and animals. To decrease the use of chemical methods green synthesis and stabilization of metallic nanomaterials viable option. Biosurfactants can potentially replace virtually any synthetic they are extracellular compounds produced by microbes such as by bacteria and grown on different carbon sources containing hydrophobic/hydrophilic substrates. The biosurfactants have a wide variety of chemical structures and surface properties and among them is the ... (Complete abstract click electronic access below) / Doutor

The current and forecasted global consumption of plastic packaging and products through the 21st century combined with the already reported and growing negative impact of plastics on the environment due to plastics being synthesized from nonrenewable resources that do not biodegrade is of serious concern. However, recent advances in starch technology including the development of thermoplastic starch (TPS) materials —polymers that are both renewable and biodegradable—have brought hope to reducing this impact. The mechanical properties of thermoplastic starch have often been improved by blending with synthetic polymers. One issue that arises with blending is volatilization of the melt from moisture in the TPS materials. Ecostarch™ a proprietary, pelletized thermoplastic starch resin formulated from potato starch, was processed and tested to observe injection molding processability at various moisture levels, in pure TPS as well as various blend ratios with high-density polyethylene (HDPE) and polypropylene (PP). This study evaluated and analyzed the effects of the TPS pellet moisture content on void formation in the plastic pre-injection melt and subsequent molded part mechanical properties. Statistical analysis of the test results showed that moisture had a significant effect on void formation in the plastic melt. In TPS/HDPE blends, voids percent (as measured by cross section area) increased by 300-350% from 0.6% to 1.4% moisture levels. In unblended TPS, void percent increased by 150% from 0.4% to 1.4% moisture levels. In the unblended TPS parts, impact strength (energy in ft-lb) was decreased by 1% from 0.6% to 1.4% moisture level. In the TPS/HDPE and TPS/PP blends, there was no significant effect on impact strength due to the moisture percent levels of the TPS. Modulus decreased by 25% from 0.4% to 1.4% moisture level in unblended TPS parts. From 0.6% to 1.4% change in TPS moisture content, the modulus of the TPS/HDPE blend decreased by 9% at a 30% TPS/70% HDPE blend and decreased by 14% at a 70% TPS/30% HDPE blend. Though the moisture of TPS did not have a significant impact on the tensile strength of TPS/HDPE blends, the tensile strength of TPS/PP blend samples were significantly affected: a change from 0.6% to 1.4% moisture increased tensile strength 34% at a 70% TPS/30% PP blend and increased tensile strength by 22% at a 30% TPS/70% PP blend. Thus the results of this study highlight the relationships between moisture, voids, and mechanical performance of TPS and TPS/Polymer blends.

Det slängs bröd i svenska matvarubutiker i Sverige samtidigt som läderproduktion är miljöförstörande. För att mildra miljöpåverkan av konventionell lädertillverkning och matsvinn i matvarubutiker odlades filamentös svamp på brödrester för att användas som ett miljövänligt alternativ till animaliskt läder. Detta arbete undersöker ifall en ny typ av läder-liknande material kan förbättras genom att tillsätta växt-tanniner och andra naturliga ämnen till filamentös svampbiomassa vid olika steg i tillverkningsprocessen. Den filamentösa svampen Rhizopus delemar odlades med hydrolyserade brödrester från matvarubutiker som substrat, och fyra olika växt-tanniner tillsattes odlingsmediumen (Tara, Myrobalan, Quebracho, Kastanje). Av de tannin-behandlade biomassorna uppvisade material som behandlats med tara tannin efter skörd av biomassan mest läderliknande mekaniska egenskaper (dragstyrka och förlängning) medan ren, obehandlad biomassa uppvisade högst dragstyrka av alla testade material. Additionen av tanniner ökade töjningsförmågan samtidigt som dragstyrkan minskade hos de resulterande materialen. Behandling med den naturliga tvärbindaren genipin resulterade i ökad dragstyrka och förlängning för flera av materialen. Resultat från HPLC analys av odlingsmediet med tara tannin indikerade även att Rhizopus delemar använde tanninet som substrat. / Bread is thrown away in Swedish grocery stores in Sweden at the same time as leather production is environmentally destructive. In order to mitigate the environmental impact of conventional leather making and to reduce food waste, fungal mycelium was grown on bread waste to be utilized as an eco-friendly leather substitute. This work investigates whether this new type of leather-like material can be improved by adding vegetable tannins and other natural compounds to filamentous fungal biomass at different stages of the production process. The filamentous fungus Rhizopus delemar was grown in shake flasks with hydrolyzed bread as substrate and four different plant tannins were added to the growth mediums. (Tara, Myrobalan, Quebracho, Chestnut). Tara and myrobalan were not inhibitory for growth during the shake flask cultivation, so they were further used in a scaled-up cultivation using 4 L bubble column reactors. However, myrobalan tannin was inhibitory when cultivating in 4 L bubble column reactors. Out of the tannin-treated biomasses, materials treated with tara tannin post cultivation exhibited the highest mechanical properties (tensile strength and elongation), while pure, untreated biomass exhibited the highest tensile strength of all materials tested. Overall, the addition of tannins to the biomasses increased the elongational capacities while lowering the tensile strengths. Treatment with the natural crosslinking-agent genipin resulted in increased average tensile strength and elongation at break for several of the materials tested. Furthermore, HPLC analysis of culture medium containing tara tannin indicated that Rhizopus delemar was able to metabolize the tannin and use it as a substrate.

Environmentally friendly lubricants are in demand in response to the rising concerns and restrictive legislation that surround the use of mineral oil lubricants. One area of importance is understanding the service life of the environmentally friendly base oils of these non-toxic, biodegradable and renewable alternatives. The service life of a lubricant is directly influenced by its degradation behavior, especially oxidation.  In this research, selected environmentally friendly base oils; Glycerol, Rapeseed oil, Polypropylene glycol, Polyethylene glycol, Bis(di-2-ethyl hexyl) sebacate, Squalene and reference mineral oil; paraffin,  were subjected to thermo-oxidative ageing at 150oC. The changes in the chemical structures of the samples were followed using Spectroscopic, chromatographic, rheological and corrosivity studies. Tribological tests were also carried out to quantify the changes in these lubricants. The results obtained showed that the thermal oxidation affected the physicochemical properties and the lubricating ability of the base oils. However, each base oil degraded distinctly to the accelerated ageing conditions.

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The field of soft electronics is rapidly growing as there is an increased demand for health monitoring using wearable electronics that conforms to biological tissue. To promote sustainability and reduce electronic waste, it is of interest to find ways to reuse low-value-added commodities, such as protein-rich byproducts, for materials in high-value-added technologies that are degradable at end of use. One recognised byproduct from meat production is the abundant protein collagen, or the hydrolysed derivative gelatine. To overcome the limited mechanical properties of gelatine, it can be functionalised with a polymer with previous use in tissue-engineering and battery encapsulation, namely Poly(Glycerol Sebacate)(PGS), to generate the copolymer PGS-G. The work described in this thesis focuses on PGS and PGS-G polymer characterisation by utilising ATR-FTIR and DSC, but also on material characterisation of mechanical and hydration properties, ionic conductivity, and degradation. The results indicate that the successfully synthesised PGS and PGS-G polymers should not be crosslinked completely to achieve the most flexible mechanical properties, but also that crosslinking density should be tuned to suit the application. Moreover, incorporation of gelatine in PGS resulted in increased hydrophilicity for PGS-G. Finally, it was concluded that PGS is suitable for encapsulation whereas PGS-G could be used as an active component. Future work should include degradation studies in vivo and under environmental aerobic conditions to ensure that the polymers are fully biodegradable. / Mjuk elektronik är ett nytt forskningsområde som utvecklas starkt i takt med den ökade efterfrågan på hälsoövervakning med innovativ elektronik som är mjuk och töjbar vilket möjliggör smidig integrering i biologisk vävnad. För att främja hållbarhet och minska elektroniskt avfall så är det av intresse att återanvända lågt värderade handelsvaror, såsom proteinrika restprodukter från industrin, till att skapa funktionella material för värdeskapande teknologier vilka är nedbrytbara efter användning. En välkänd restprodukt från köttproduktion är proteinet kollagen och dess hydrolyserade derivat gelatin. För att förbättra de mekaniska egenskaperna hos gelatin så kan det funktionaliseras med en polymer, vid namn Poly(Glycerol Sebacate)(PGS), som tidigare har använts för att skapa substitut till biologisk vävnad och batteriinkapsling. Denna reaktion genererar den nya polymeren PGS-G. I det här examensarbetet beskrivs karaktärisering av polymererna PGS och PGS-G, som utfördes med ATR-FTIR och DSC, samt karaktärisering av materialets mekaniska och hydrerande egenskaper men även dess ledningsförmåga och nedbrytbarhet. Resultaten indikerar att polymererna PGS och PGS-G ej bör tvärbindas fullständigt för att uppnå optimala mekaniska egenskaper med avseende på flexibilitet men också att tvärbindningen ska justeras beroende på tillämpningen. Vidare bidrar inkorporeringen av gelatin i PGS till en ökad hydrofilicitet i PGS-G. Slutligen visades det att PGS är lämpligt för inkapsling medan PGS-G kan användas som en aktiv komponent. Innan tillämpning behöver ytterligare studier genomföras med avseende på nedbrytbarhet, dels in vivo, dels i aerobiska förhållanden, för att säkerhetsställa att polymererna är fullständigt nedbrytbara.

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